Hydroxy-substituted N-alkoxy hindered amines and compositions stabilized therewith

ABSTRACT

Hindered amines substituted on the N-atom with an —O—E—OH moiety are particularly effective in stabilizing polyolefin and automotive coating compositions against the deleterious effects of oxidative, thermal and actinic radiation where the presence of the OH group on the compounds adds important properties not attainable by the use of normal —O—E moieties.

This is a divisional of application Ser. No. 09/257,711, filed on Feb.25, 1999, now U.S. Pat. No. 6,271,377.

The instant invention pertains to hindered amine compounds which aresubstituted on the N-atom by N-alkoxy moieties containing one to threehydroxyl groups. These materials are particularly effective instabilizing polyolefins, especially thermoplastic polyolefins, againstthe deleterious effects of oxidative, thermal and actinic radiation. Thecompounds are also effective in stabilizing acid catalyzed and ambientcured coatings systems.

BACKGROUND OF THE INVENTION

4-Hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine and4-oxo-1-oxyl-2,2,6,6-tetramethylpiperidine are reported to have beenused to trap carbon centered radicals formed from methanol, ethanol,isopropanol and sec-butanol by S. Nigam et al., J. Chem. Soc., Trans.Faraday Soc. 1, 1976, 72, 2324 and by K.-D. Asmus et al., Int. J.Radiat. Biol., 1976, 29, 211.

U.S. Pat. No. 5,627,248 and European Patent Application No. 135,280 A2describe, respectively, difunctional and monofunctional living freeradical polymerization initiators, some of which contain hindered amineethers substituted by hydroxy groups. These compounds differsubstantially in structure and performance from the instant compounds.

European Patent Application No. 427,672 A1 and U.S. Pat. No. 4,972,009mention, but do not exemplify, respectively, hydroxylamine and nitronestructures, some of which contain C₁-C₄ hydroxyalkoxy substituted2,2,6,6-tetramethylpiperidine derivatives. Such structures are outsidethe scope of the instant invention.

U.S. Pat. No. 5,204,473 describes N-hydrocarbyloxy hindered aminederivatives that are prepared exclusively from organic compoundscontaining only carbon and hydrogen atoms. Such compounds arestructurally quite different from the instant compounds.

U.S. Pat. No. 5,004,770 describes hindered amine compounds which aresubstituted on the N-atom by alkoxy moieties which alkoxy groups arethemselves unsubstituted. These compounds are especially useful inpolymers including polybutadiene, polystyrene, ABS, polyacetal,polyamide, polyester, polyurethane and polycarbonate.

U.S. Pat. No. 5,096,950 also describes hindered amine compounds whichare substituted on the N-atom by alkoxy moieties which alkoxy groups arethemselves unsubstituted, These compounds are found to be useful inpolyolefins.

The instant compounds are N-alkoxy substituted derivatives of2,2,6,6-tetraalkylpiperidines where the alkoxy group is substituted byone to three hydroxy moieties. The instant compounds also compriseN-alkoxy bridged derivatives of the 2,2,6,6-tetraalkylpiperidines wherethe alkoxy moiety, which is substituted by one to three hydroxy groups,is shared by two hindered amine molecules. The free hydroxy moieties ofthese compounds may be reacted with carboxylic acids, acid chlorides oresters to form simple esters or polyesters, or with isocyanates to formurethanes or polyurethanes.

The instant compounds, because of their low bascity which is shared bythe simple unsubstituted N-alkoxy compounds cited in the two patentsmentioned above, are of particular value in the stabilization ofpolyolefins and automotive coating compositions where the activity ofthe more basic hindered amine stabilizes is significantly reducedbecause of interaction with the polymer substrate or acid catalyticsystem needed for curing such substrate.

Examples of polyolefin compositions in which the instant compounds areeffective include flame retardant polyolefins where acidic residues fromthe decomposition of the halogenated flame retardants deactivatehindered amines not having the N—OR group, greenhouse films andagricultural mulch films where acidic residues from pesticides interferewith the activity of “normal” hindered amine stabilizers, and inthermoplastic polyolefins where pigment interactions with basic hinderedamine stabilizers interfere with painting the substrate surfaces.Examples of coating compositions in which the instant compounds areeffective include melamine crosslinked thermoset acrylic resins, whichare cured using strong acids that interact with basic hindered aminestabilizers. The instant compounds are also effective in acrylic alkydor polyester resins with isocyanate crosslinking agents, and in epoxyresins with carboxylic acid, anhydride, or amine crosslinking agents.

While the unsubstituted N-OR compounds described in U.S. Pat. Nos.5,004,770 and 5,096,950 also perform well in the compositions describedin the paragraph above, the instant compounds differ significantly inboth structure and in performance from the prior art compounds by virtueof the presence of the one to three free hydroxy groups present on theN-alkoxy moiety. These hydroxyl groups in the instant compounds providesaid compounds with superior antistatic properties, compatibility inmore polar environments such as polyurethane based and in water-bomeautomotive coating systems, and in stabilizing painted automotivethermoplastic olefin structures.

The instant compounds are particularly suited for

(a) providing superior compatibility in polycarbonates andpolycarbonate/ABS blends compared to the N—OE prior art compounds; and

(b) providing superior compatibility in polyesters and polyamidescompared to the prior art N—OE compounds.

OBJECTS OF THE INVENTION

There are two objects to the instant invention which are:

1. Novel compounds having on the 1-position of the hindered amine amoiety —O—E—OH where the OH group provides important properties; and

2. Compositions stabilized by the novel compounds described above.

DETAILED DISCLOSURE

The instant invention pertains to novel compounds having 1-alkoxysubstituted hindered amine derivatives where the alkoxy moiety issubstituted by one to three hydroxy groups as described in formulas (1)to (15); or to novel compounds having 1-alkoxy bridged hindered aminederivatives where the alkoxy moiety, substituted by one to three hydroxygroups, is shared by two hindered amine molecules as described informulas (16) to (28); or to oligomeric or polymeric hindered aminemolecules made from the reaction of dialkyl esters or isocyanates withhydroxy substituted N-alkoxy derivatives of4-hydroxy-2,2,6,6-tetraalkylpiperidine as described in formula (29); orto simple diester or urethane derivatives of hydroxy substitutedN-alkoxy derivatives of 4-hydroxy-2,2,6,6-tetramethylpiperidine asdescribed in formula (30)

G₁ and G₂ are independently alkyl of 1 to 4 carbon atoms, or G₁ and G₂together are pentamethylene; preferably G₁ and G₂ are each methyl;

E is a straight or branched chain alkylene of 1 to 18 carbon atoms,cycloalkylene of 5 to 18 carbon atoms, cycloalkenylene of 5 to 18 carbonatoms, a straight or branched chain alkylene of 1 to 4 carbon atomssubstituted by phenyl or by phenyl substituted by one or two alkylgroups of 1 to 4 carbon atoms;

b is 1, 2 or 3 with the proviso that b cannot exceed the number ofcarbon atoms in E or L, and when b is 2 or 3, each hydroxyl group isattached to a different carbon atom of E or L; the two hindered aminegroups are generally, but not always, attached to two different carbonatoms of L;

in each of the formulas (1) to (15)

m is 0 or 1;

R₁ is hydrogen, hydroxyl or hydroxymethyl;

R₂ is hydrogen, alkyl of 1 to 12 carbon atoms or alkenyl of 2 to 12carbon atoms;

n is 1 to 4;

when n is 1,

R₃ is alkyl of 1 to 18 carbon atoms, alkoxycarbonylalkylenecarbonyl of 4to 18 carbon atoms, alkenyl of 2 to 18 carbon atoms, glycidyl,2,3-dihydroxypropyl, 2-hydroxy or 2-(hydroxymethyl) substituted alkyl of3 to 12 carbon atoms which alkyl is interrupted by oxygen, an acylradical of an aliphatic or unsaturated aliphatic carboxylic or carbamicacid containing 2 to 18 carbon atoms, an acyl radical of acycloaliphatic carboxylic or carbamic acid containing 7 to 12 carbonatoms, or acyl radical of an aromatic acid containing 7 to 15 carbonatoms;

when n is 2,

R₃ is alkylene of 2 to 18 carbon atoms, a divalent acyl radical of analiphatic or unsaturated aliphatic dicarboxylic or dicarbamic acidcontaining 2 to 18 carbon atoms, a divalent acyl radical of acycloaliphatic dicarboxylic or dicarbamic acid containing 7 to 12 carbonatoms, or a divalent acyl radical of an aromatic dicarboxylic acidcontaining 8 to 15 carbon atoms;

when n is 3,

R₃ is a trivalent acyl radical of an aliphatic or unsaturated aliphatictricarboxylic acid containing 6 to 18 carbon atoms, or a trivalent acylradical of an aromatic tricarboxylic acid containing 9 to 15 carbonatoms;

when n is 4,

R₃ is a tetravalent acyl radical of an aliphatic or unsaturatedaliphatic tetracarboxylic acid, especially 1,2,3,4-butanetetracarboxylicacid, 1,2,3,4-but-2-enetetracarboxylic acid,1,2,3,5-pentanetetracarboxylic acid and 1,2,4,5-pentanetetracarboxylicacid, or R₃ is a tetravalent acyl radical of an aromatic tetracarboxylicacid containing 10 to 18 carbon atoms;

p is 1to3,

R₄ is hydrogen, alkyl of 1 to 18 carbon atoms or acyl of 2 to 6 carbonatoms;

when p is 1,

R₅ is hydrogen, alkyl of 1 to 18 carbon atoms, an acyl radical of analiphatic or unsaturated aliphatic carboxylic or carbamic acidcontaining 2 to 18 carbon atoms, an acyl radical of a cycloaliphaticcarboxylic or carbamic acid containing 7 to 12 carbon atoms, an acylradical of an aromatic carboxylic acid containing 7 to 15 carbon atoms,or R₄ and R₅ together are —(CH₂)₅CO—, phthaloyl or a divalent acylradical of maleic acid;

when p is 2,

R₅ is alkylene of 2 to 12 carbon atoms, a divalent acyl radical of analiphatic or unsaturated aliphatic dicarboxylic or dicarbamic acidcontaining 2 to 18 carbon atoms, a divalent acyl radical of acycloaliphatic dicarboxylic or dicarbamic acid containing 7 to 12 carbonatoms, or a divalent acyl radical of an aromatic dicarboxylic acidcontaining 8 to 15 carbon atoms;

when p is 3,

R₅ is a trivalent acyl radical of an aliphatic or unsaturated aliphatictricarboxylic acid containing 6 to 18 carbon atoms, or a trivalent acylradical of an aromatic tricarboxylic acid containing 9 to 15 carbonatoms;

when n is 1,

R₆ is alkoxy of 1 to 18 carbon atoms, alkenyloxy of 2 to 18 carbonatoms, —NHalkyl of 1 to 18 carbon atoms or —N(alkyl)₂ of 2 to 36 carbonatoms,

when n is 2,

R₆ is alkylenedioxy of 2 to 18 carbon atoms, alkenylenedioxy of 2 to 18carbon atoms, —NH-alkylene-NH— of 2 to 18 carbon atoms or—N(alkyl)-alkylene-N(alkyl)— of 2 to 18 carbon atoms, or R₆ is4-methyl-1,3-phenylenediamino,

when n is 3,

R₆ is a trivalent alkoxy radical of a saturated or unsaturated aliphatictriol containing 3 to 18 carbon atoms,

when n is 4,

R₆ is a tetravalent alkoxy radical of a saturated or unsaturatedaliphatic tetraol containing 4 to 18 carbon atoms,

R₇ and R₈ are independently chlorine, alkoxy of 1 to 18 carbon atoms,—O—T₁, amino substituted by 2-hydroxyethyl, —NH(alkyl) of 1 to 18 carbonatoms, —N(alkyl)T₁ with alkyl of 1 to 18 carbon atoms, or —N(alkyl)₂ of2 to 36 carbon atoms,

R₉ is a divalent oxygen atom, or R₉ is a divalent nitrogen atomsubstituted by either hydrogen, alkyl of 1 to 12 carbon atoms or T₁

R₁₀ is hydrogen or methyl,

q is 2 to 8,

R₁₁ and R₁₂ are independently hydrogen or the group T₂

R₁₃ is hydrogen, phenyl, straight or branched alkyl of 1 to 12 carbonatoms, alkoxy of 1 to 12 carbon atoms, straight or branched alkyl of 1to 4 carbon atoms substituted by phenyl, cycloalkyl of 5 to 8 carbonatoms, cycloalkenyl of 5 to 8 carbon atoms, alkenyl of 2 to 12 carbonatoms, glycidyl, allyloxy, straight or branched hydroxyalkyl of 1 to 4carbon atoms, or silyl or silyloxy substituted three times independentlyby hydrogen, by phenyl, by alkyl of 1 to 4 carbon atoms or by alkoxy of1 to 4 carbon atoms;

R₁₄ is hydrogen or silyl substituted three times independently byhydrogen, by phenyl, by alkyl of 1 to 4 carbon atoms or by alkoxy of 1to 4 carbon atoms;

d is 0 or 1;

h is 0 to 4;

k is 0 to 5;

x is 3to6;

y is 1to10;

z is an integer such that the compound has a molecular weight of 1000 to4000 amu,

R₁₅ is morpholino, piperidino, 1-piperizinyl, alkylamino of 1 to 8carbon atoms, especially branched alkylamino of 3 to 8 carbon atoms suchas tert-octylamino, —N(alkyl)T₁ with alkyl of 1 to 8 carbon atoms, or—N(alkyl)₂ of 2 to 16 carbon atoms,

R₁₆ is hydrogen, acyl of 2 to 4 carbon atoms, carbamoyl substituted byalkyl of 1 to 4 carbon atoms, s-triazinyl substituted once by chlorineand once by R₁₅, or s-triazinyl substituted twice by R₁₅ with thecondition that the two R₁₅ substituents may be different;

R₁₇ is chlorine, amino substituted by alkyl of 1 to 8 carbon atoms or byT₁, —N(alkyl)T₁ with alkyl of 1 to 8 carbon atoms, —N(alkyl)₂ of 2 to 16carbon atoms, or the group T₃

R₁₈ is hydrogen, acyl of 2 to 4 carbon atoms, carbamoyl substituted byalkyl of 1 to 4 carbon atoms, s-triazinyl substituted twice by—N(alkyl)₂ of 2 to 16 carbon atoms or s-triazinyl substituted twice by—N(alkyl)T₁ with alkyl of 1 to 8 carbon atoms;

L is straight or branched chain alkylene of 1 to 18 carbon atoms,cycloalkylene of 5 to 8 carbon atoms, cycloalkenylene of 5 to 8 carbonatoms, alkenylene of 3 to 18 carbon atoms, a straight or branched chainalkylene of 1 to 4 carbon atoms substituted by phenyl or by phenylsubstituted by one or two alkyl of 1 to 4 carbon atoms,

in formulas (16) to (28), R₁, R₂, R₇, R₈, R₉, R₁₀, R₁₃, R₁₄, d,h, k, m,q, and T₁ have the same meanings as in formulas (1) to (15);

R₁₉ is hydrogen, alkyl of 1 to 18 carbon atoms, alkenyl of 2 to 18carbon atoms, glycidyl, 2,3-dihydroxypropyl, 2-hydroxy or2-(hydroxymethyl) substituted alkyl of 3 to 12 carbon atoms which alkylis interrupted by oxygen, an acyl radical of an aliphatic or unsaturatedaliphatic carboxylic or carbamic acid containing 2 to 18 carbon atoms,an acyl radical of a cycloaliphatic carboxylic or carbamic acidcontaining 7 to 12 carbon atoms, or acyl radical of an aromatic acidcontaining 7 to 15 carbon atoms;

R₂₀ is alkylene of 2 to 18 carbon atoms, a divalent acyl radical of analiphatic or unsaturated aliphatic dicarboxylic or dicarbamic acidcontaining 2 to 18 carbon atoms, a divalent acyl radical of acycloaliphatic dicarboxylic or dicarbamic acid containing 7 to 12 carbonatoms, or a divalent acyl radical of an aromatic dicarboxylic acidcontaining 8 to 15 carbon atoms;

R₂₁ is hydrogen, alkyl of 1 to 18 carbon atoms or acyl of 2 to 6 carbonatoms;

R₂₂ is hydrogen, alkyl of 1 to 18 carbon atoms, an acyl radical of analiphatic or unsaturated aliphatic carboxylic or carbamic acidcontaining 2 to 18 carbon atoms, an acyl radical of a cycloaliphaticcarboxylic or carbamic acid containing 7 to 12 carbon atoms, an acylradical of an aromatic carboxylic acid containing 7 to 15 carbon atoms,or R₄ and R₈ together are —(CH₂)₅CO—, phthaloyl or a divalent acylradical of maleic acid;

R₂₃ is hydrogen, alkyl of 1 to 4 carbon atoms or acyl of 2 to 6 carbonatoms;

R₂₄ is alkylene of 2 to 18 carbon atoms, a divalent acyl radical of analiphatic or unsaturated aliphatic dicarboxylic or dicarbamic acidcontaining 2 to 18 carbon atoms, a divalent acyl radical of acycloaliphatic dicarboxylic or dicarbamic acid containing 7 to 12 carbonatoms, or a divalent acyl radical of an aromatic dicarboxylic acidcontaining 8 to 15 carbon atoms;

R₂₅ is alkoxy of 1 to 18 carbon atoms, alkenyloxy of 2 to 18 carbonatoms, —NHalkyl of 1 to 18 carbon atoms or —N(alkyl)₂ of 2 to 36 carbonatoms,

R₂₆ is alkylenedioxy of 2 to 18 carbon atoms, alkenylenedioxy of 2 to 18carbon atoms, —NH-alkylene—NH— of 2 to 18 carbon atoms or—N(alkyl)-alkylene-N(alkyl)— of 3 to 18 carbon atoms,

in formulas (29) and (30), G is a carbon centered diradical derived froma primary, secondary or tertiary alcohol G—OH, where

z is as defined above, and

G is straight or branched chain alkylene of 1 to 18 carbon atoms,cycloalkylene of 5 to 8 carbon atoms, cycloalkenylene of 5 to 8 carbonatoms, alkenylene of 3 to 18 carbon atoms, a straight or branched chainalkylene of 1 to 4 carbon atoms substituted by phenyl or by phenylsubstituted by one or two alkyl of 1 to 4 carbon atoms, with the provisothat in formula (29) successive hindered amine moieties can be orientedin either a head to head or head to tail fashion;

R₂₇ is a straight or branched chain alkylene of 1 to 18 carbon atoms,cycloalkylene or cycloalkenylene of 5 to 8 carbon atoms, phenylene or—NH-alkylene-NH— of 2 to 18 carbon atoms including5-amino-1-aminomethyl-1,3,3-trimethylcyclohexane and —NH-xylylene-NH—;

R₂₈ is alkyl of 1 to 4 carbon atoms;

R₂₉ is a straight or branched chain alkyl or —NH-alkyl of 1 to 18 carbonatoms or —NH-cycloalkyl of 5 to 8 carbon atoms; and

with the further proviso that in formulas (1) and (2), when b is 1, E isnot methyl, ethyl, 2-propyl or 2-methyl-2-propyl.

Preferably, G₁ and G₂ are each methyl.

Preferably, in formulas (1) to (28), b is 1 or 2, most preferably 1.

When b is 1, E—OH and L—OH are respectively a carbon-centered radical ordiradical formed preferably from 2-methyl-2-propanol, 2-propanol,2,2-dimethyl-1-propanol, 2-methyl-2-butanol, ethanol, 1-propanol,1-butanol, 1-pentanol, 1-hexanol, 1-nonanol, 1-decanol, 1-dodecanol,1-octadecanol, 2-butanol, 2-pentanol, 2-ethyl-1-hexanol, cyclohexanol,cyclooctanol, allyl alcohol, phenethyl alcohol or 1-phenyl-1-ethanol;most preferably E—OH and L—OH are formed from 2-methyl-2-propanol orcyclohexanol.

When b is 2, E—OH and L—OH are respectively a carbon-centered radical ordiradical formed preferably from 1,2-ethanediol, 1,2-propanedial,1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol,2,2-dimethyl-1,3-propanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediolor 1,4-cyclohexanediol; most preferably E—OH and L—OH are formed from1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,2-cyclohexanediol,1,3-cyclohexanediol or 1,4-cyclohexanediol.

When b is 3, E—OH and L—OH are respectively a carbon-centered radical ordiradical formed from glycerol, 1,1,1-tris(hydroxymethyl)methane,2-ethyl-2-(hydroxymethyl-1,3-propanediol, 1,2,4-butanetriol or1,2,6-hexanetriol; most preferably E—OH and L—OH are formed fromglycerol, 1,1,1-tris(hydroxymethyl)methane,2-ethyl-2-(hydroxymethyl-1,3-propanediol.

Preferably in formulas (29) and (30), —G—O— is formed from ethanol,phenethyl alcohol, cyclohexanol or 2-methyl-2-propanol (=tert-butylalcohol).

Preferably in formula (3), m is 0, R₁ is hydrogen or hydroxymethyl, andR₂ is hydrogen; or m is 1, R₁ is hydroxy or hydroxymethyl, and R₂ ishydrogen, methyl or ethyl.

Preferably in formula (5), R₂ is hydrogen or dodecyl.

Preferably in formula (6), n is 1 or 2, and when n is 1, R₃ is allyl,glycidyl, acryloyl, methacryloyl, octadecanoyl, hexadecanoyl,tetradecanoyl, methoxycarbonylpropionyl, methoxycarbonylbutyryl,methoxycarbonylpentanoyl or methoxycarbonylnonanoyl; or when n is 2, R₃is succinyl, glutaryl, adipoyl, sebacoyl, 1,6-hexanedicarbamoyl or cis-or trans-5-carbamoyl-1-(carbamoylmethyl)-1,3,3-trimethylcyclohexane.

Preferably in formula (7), p is 1 or 2, and when p is 1, R₄ is hydrogenand R₅ is butyl; or R₄ and R₅ together are the divalent acyl radical ofmaleic acid; or when p is 2, R₄ is hydrogen or acetyl, and R₅ is1,6-hexanediyl.

Preferably in formula (8), n is 1 or 2, and when n is 1, R₆ is ethoxy,6-methyl-1-heptyloxy, ethylamino, butylamino or octylamino; or when n is2, R₆ is 1,2-ethanedioxy, 1,4-butanedioxy, ethylenediamino,hexamethylenediamino, or 4-methyl-1,3-phenylenediamino.

Preferably in formula (9), R₇ and R₈ are independently chlorine,octylamino, tert-octyl-amino or amino substituted by T₁ and ethyl, butylor dodecyl; and R₉ is a divalent nitrogen atom substituted by ethyl,butyl or dodecyl.

Preferably in formula (10), q is 2, 4 or 6, R₇ is chlorine, octylamino,octadecylamino or amino substituted by T₁ and ethyl, butyl or dodecyl;and R₁₀ is hydrogen.

Preferably in formula (11), n is 3, p is 2, R₂ is ethyl, butyl ordodecyl; and one of R₁₁ or R₁₂ is T₂, and the other is hydrogen.

Preferably in formula (12), k is 3, R₉ is a divalent oxygen atom or is adivalent nitrogen atom substituted by ethyl, butyl or dodecyl, R₁₃ ishydrogen or methyl, and when d is 0, x is 5 or 6, and when d is 1, x is3 or 4.

Preferably in formula (13), d is 0 or 1, h is 0-2, k is 0 or 3, y is1-8, R₉ is a divalent oxygen atom or a divalent nitrogen atomsubstituted by ethyl, butyl or dodecyl, R₁₃ is hydrogen, methyl, ethyl,methoxy or ethoxy, and R₁₄ is hydrogen or trimethylsilyl.

Preferably in formula (14), R₉ is a divalent oxygen atom, R₁₀ ishydrogen or methyl, m is 0 and z is an integer such that the molecularweight of the compound is 1500-3000 amu.

Preferably in formula (15) q is 6, y is 1-7, R₁₅ is tert-octylamino,morpholino, amino substituted by T₁ and butyl, which may also bedesignated as T₁-butylamino, R₁₆ is hydrogen, acetyl, ethylcarbamoyl,2,4-bis(dibutylamino)-s-triazinyl, 2,4-bis(diethylamino)-s-triazinyl,s-triazinyl substituted twice by T₁-butylamino or s-triazinylsubstituted once by diethylamino or dibutylamino and once byT₁-butylamino, R₁₇ is dibutylamino, diethylamino, T₁-butylamino or R₁₇is T₃ where R₁₈ is acetyl or ethylcarbamoyl.

Preferably in formula (17), m is 0, R₁ is hydrogen or hydroxymethyl, andR₂ is hydrogen; or m is 1, R₁ is hydroxy or hydroxymethyl, and R₂ ishydrogen or methyl.

Preferably in formula (19), R₂ is hydrogen or dodecyl.

Preferably in formula (20), R₁₉ is hydrogen, allyl, acryloyl,methacryloyl, octadecanoyl or hexadecanoyl.

Preferably in formula (21), R₂₀ is succinyl, glutaryl, adipoyl,sebacoyl, 1,6-hexanedicarbamoyl, or cis- ortrans-5-carbamoyl-1-(carbamoylmethyl)-1,3,3-trimethylcyclohexane.

Preferably in formula (22), R₂₁ is hydrogen and R₂₂ is hydrogen orbutyl; or R₂₁ and R₂₂ together are the divalent acyl radical of maleicacid.

Preferably in formula (23), R₂₃ is hydrogen or acetyl, and R₂₄ isethylene or hexamethylene.

Preferably in formula (24), R₂₅ is ethoxy, 6-methyl-1-heptyloxy,ethylamino, butylamino or octylamino.

Preferably in formula (25), R₂₆ is 1,2-ethanedioxy, 1-4-butanedioxy,ethylenediamino or hexamethylenediamino.

Preferably in formula (26), R₇ and R₈ are independently chlorine,octylamino, tert-octyl-amino, octadecylamino, T₁-ethylamino,T₁-butylamino or T₁-dodecylamino, and R₉ is a divalent nitrogen atomsubstituted by ethyl, butyl or dodecyl.

Preferably in formula (27), q is 2, 4 or 6, R₇ is chlorine, octylamino,octadecylamino, T₁-ethylamino, T₁-butylamino or T₁-dodecylamino, and R₁₀is hydrogen.

Preferably in formula (28), d is 0 or 1, h is 0-2, k is 0 or 3, R₉ is adivalent oxygen atom or a divalent nitrogen atom substituted by ethyl,butyl or dodecyl, R₁₃ is hydrogen, methyl, ethyl, methoxy or ethoxy, andR₁₄ is hydrogen or trimethylsilyl.

Preferably in formula (29), R₂₇ is ethylene, trimethylene,tetramethylene, octamethylene, 1,6-diaminohexane or5-amino-1-aminomethyl-1,3,3-trimethylcyclohexane; z is an integer suchthat the molecular weight of the compound is 1500-3000 amu, R₂₈ ismethyl or ethyl, and G is ethylene, 1,2-cyclohexanediyl,1,3-cyclohexanediyl, 1,4-cyclohexanediyl, —CH(C₆H₅)CH₂— or —CH₂C(CH₃)₂—.

Preferably in formula (30), R₂₉ is pentadecyl, heptadecyl, butylamino orcyclohexylamino.

Still more preferred embodiments of the instant invention are thecompounds of formulas (1) to (30) where E—OH, L—OH and G—O— are formedfrom 2-methyl-2-propanol (=tert-butyl alcohol) or cyclohexanol.

Most preferably in formula (6), when n is 1, R₃ is acryloyl,methacrloyl, glycidyl, octadecanoyl, hexadecanoyl,methoxycarbonylpropionyl, methoxycarbonylbutyryl,methoxycarbonylpentanoyl or methoxycarbonylnonanoyl; or when n is 2, R₃is succinyl, glutaryl, adipoyl, sebacoyl, 1,6-hexanedicarbamoyl or cis-or trans-5-carbamoyl-1-(carbamoylmethyl)-1,3,3-trimethylcyclohexane.

Most preferably in formula (7), p is 1 or 2, and when p is 1, R₄ ishydrogen and R₅ is hydrogen or butyl; or when p is 2, R₄ is hydrogen,and R₅ is 1,6-hexanediyl.

Most preferably in formula (9), R₇ is chlorine, octylamino orT₁-butylamino, R₈ is chlorine or T₁-butylamino, and R₉ is a divalentnitrogen atom substituted by butyl.

Most preferably in formula (10), q is 6, R₇ is T₁-butylamino; and R₁₀ ishydrogen.

Most preferably in formula (11), n is 3, p is 2, and one of R₁₁ or R₁₂is T₂, and the other is hydrogen.

Most preferably in formula (12), k is 3, R₉ is a divalent oxygen atom,R₁₃ is hydrogen or methyl, and d is 0, x is 5 or 6, and when d is 1, xis 3 or 4.

Most preferably in formula (13), d is 0 or 1, h is 0-2, k is 0 or 3, yis 1-8, R₉ is a divalent oxygen atom, R₁₃ is hydrogen, methyl, ethyl,methoxy or ethoxy, and R₁₄ is hydrogen or trimethylsilyl.

Most preferably in formula (15) q is 6, y is 1-7, R₁₅ is T₁-butylamino,R₁₆ is hydrogen, acetyl, ethylcarbamoyl,2,4-bis(dibutylamino)-s-triazinyl, 2,4-bis(diethylamino)-s-triazinyl,s-triazinyl substituted twice by T₁-butylamino or s-triazinylsubstituted once by diethylamino or dibutylamino and once byT₁-butylamino, R₁₇ is dibutylamino, diethylamino, T₁-butylamino or R₁₇is T₃ where R₁ is acetyl or ethylcarbamoyl.

Most preferably in formula (20), R₁₉ is hydrogen, octadecanoyl orhexadecanoyl.

Most preferably in formula (22), R₂₁ is hydrogen and R₂₂ is hydrogen orbutyl.

Most preferably in formula (23), R₂₃ is hydrogen, and R₂₄ ishexamethylene.

Most preferably in formula (26), R₇ is chlorine, octylamino orT₁-butylamino, R₈ is chlorine or T₁-butylamino, and R₉ is a divalentnitrogen atom substituted by butyl.

Most preferably in formula (27), q is 6, R₇ is T₁-butylamino, and R₉ isa divalent nitrogen atom substituted by butyl.

Most preferably in formula (29), R₂₇ is ethylene, trimethylene,tetramethylene or octamethylene, z is an integer such that the molecularweight of the compound is 1500 to 2000 amu, and R₂₈ is methyl.

Most preferably in formula (30), R₂₉ is pentadecyl or heptadecyl.

Still more preferred embodiments of the instant invention are thecompounds of formulas (1) to (30) where E—OH, L—OH and —G—O— are formedfrom 2-methyl-2-propanol (=tert-butyl alcohol).

Especially preferred compounds of formula (6) are those where n is 1, R₃is acryloyl, methacryloyl, glycidyl, octadecanoyl, hexadecanoyl,methoxycarbonylpropionyl or methoxycarbonylbutyryl, and where n is 2, R₃is succinyl, glutaryl, adipoyl or sebacoyl.

Especially preferred compounds of formula (7) are those where R₄ ishydrogen, and when p is 1, R₅ is hydrogen or butyl, or when p is 2, R₅is hexamethylene.

Especially preferred compounds of formula (9) are those where R₇ ischlorine, octylamino or T₁-butylamino, R₈ is T₁-butylamino, and R₉ is adivalent nitrogen atom substituted by butyl.

Especially preferred compounds of formula (10) are those where q is 6,R₇ is T₁-butylamino and R₁₀ is hydrogen.

Especially preferred compounds of formula (11) are those where n is 3, pis 2, one of R₁₁ or R₁₂ is T₂ and the other is hydrogen.

Especially preferred compounds of formula (12) are those where d is 1, kis 3, x is 3 or 4, R₉ is divalent oxygen atom, and R₁₃ is methyl.

Especially preferred compounds of formula (13) are those where k is 3, yis 4-8. R₉ is a divalent oxygen atom, R₁₃ is hydrogen or methyl, d and hare 0, R₁₄ is hydrogen, or d is 1 and h is 0, and R₁₄ is trimethylsilyl.

Especially preferred compounds of formula (14) are those where m is 0,R₉ is a divalent oxygen atom, R₁₀ is hydrogen or methyl, and z is aninteger such that the molecular weight of the compound is 1500-3000 amu.

Especially preferred compounds of formula (15) are those where q is 6, yis 1-7, R₁₅ is T₁-butylamino, R₁₆ is hydrogen, acetyl, ethylcarbamoyl,2,4-bis(dibutylamino)-s-triazinyl, 2,4-bis(diethylamino)-s-triazinyl,s-triazinyl substituted twice by T₁-butylamino or s-triazinylsubstituted once by diethylamino or dibutylamino and once byT₁-butylamino, R₁₇ is dibutylamino, diethylamino, or T₃ where R₁₈ isacetyl or ethylcarbamoyl.

Especially preferred compounds of formula (20) are those where R₁₉ ishydrogen, octadecanoyl or hexadecanoyl.

Especially preferred compounds of formula (21) are those where R₂₀ issuccinyl, glutaryl, adipoyl or sebacoyl.

Especially preferred compound of formula (30) is that where R₂₉ isheptadecyl.

The instant invention also pertains to a polymer composition containingan effective stabilizing amount of one or more compounds selected fromthe compounds of formula (1) to formula (30) as described above.

Preferably, the organic material is a natural, semi-synthetic orsynthetic polymer, especially a thermoplastic polymer.

Most preferably, the polymer is a polyolefin, especially a thermoplasticpolyolefin useful in automotive coatings and applications or a urethanebased automotive coating.

The compounds of this invention exhibit superior hydrolytic stability,handling and storage stability as well as good resistance toextractability when present in a stabilized composition.

In general polymers which can be stabilized include

1. Polymers of monoolefins and diolefins, for example polypropylene,polyisobutylene, polybut-1-ene, poly4-methylpent-1-ene, polyisoprene orpolybutadiene, as well as polymers of cycloolefins, for instance ofcyclopentene or norbornene, polyethylene (which optionally can becrosslinked), for example high density polyethylene (HDPE), low densitypolyethylene (LDPE), linear low density polyethylene (LLDPE), branchedlow density polyethylene (BLDPE).

Polyolefins, i.e. the polymers of monoolefins exemplified in thepreceding paragraph, preferably polyethylene and polypropylene, can beprepared by different, and especially by the following, methods:

a) radical polymerisation (normally under high pressure and at elevatedtemperature).

b) catalytic polymerisation using a catalyst that normally contains oneor more than one metal of groups IVb, Vb, VIb or VIII of the PeriodicTable. These metals usually have one or more than one ligand, typicallyoxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenylsand/or aryls that may be either π- or σ-coordinated. These metalcomplexes may be in the free form or fixed on substrates, typically onactivated magnesium chloride, titanium(III) chloride, alumina or siliconoxide. These catalysts may be soluble or insoluble in the polymerisationmedium. The catalysts can be used by themselves in the polymerisation orfurther activators may be used, typically metal alkyls, metal hydrides,metal alkyl halides, metal alkyl oxides or metal alkyloxanes, saidmetals being elements of groups Ia, IIa and/or IIIa of the PeriodicTable. The activators may be modified conveniently with further ester,ether, amine or silyl ether groups. These catalyst systems are usuallytermed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont),metallocene or single site catalysts (SSC).

2. Mixtures of the polymers mentioned under 1), for example mixtures ofpolypropylene with polyisobutylene, polypropylene with polyethylene (forexample PP/HDPE, PP/LDPE) and mixtures of different types ofpolyethylene (for example LDPE/HDPE).

3. Copolymers of monoolefins and diolefins with each other or with othervinyl monomers, for example ethylene/propylene copolymers, linear lowdensity polyethylene (LLDPE) and mixtures thereof with low densitypolyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,propylene/butadiene copolymers, isobutylene/isoprene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers and their copolymers withcarbon monoxide or ethylene/acrylic acid copolymers and their salts(ionomers) as well as terpolymers of ethylene with propylene and a dienesuch as hexadiene, dicyclopentadiene or ethylidene-norbornene; andmixtures of such copolymers with one another and with polymers mentionedin 1) above, for example polypropylene/ethylene-propylene copolymers,LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acidcopolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or randompolyalkylene/carbon monoxide copolymers and mixtures thereof with otherpolymers, for example polyamides.

4. Hydrocarbon resins (for example C₅-C₉) including hydrogenatedmodifications thereof (e.g. tackifiers) and mixtures of polyalkylenesand starch.

5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

6. Copolymers of styrene or α-methylstyrene with dienes or acrylicderivatives, for example styrene/butadiene, styrene/acrylonitrile,styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate,styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride,styrene/acrylonitrile/methyl acrylate; mixtures of high impact strengthof styrene copolymers and another polymer, for example a polyacrylate, adiene polymer or an ethylene/propylene/diene terpolymer; and blockcopolymers of styrene such as styrene/butadiene/styrene,styrene/isoprene/styrene, styrene/ethylene/butylene/styrene orstyrene/ethylene/propylene/styrene.

7. Graft copolymers of styrene or α-methylstyrene, for example styreneon polybutadiene, styrene on polybutadiene-styrene orpolybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (ormethacrylonitrile) on polybutadiene; styrene, acrylonitrile and methylmethacrylate on polybutadiene; styrene and maleic anhydride onpolybutadiene; styrene, acrylonitrile and maleic anhydride or maleimideon polybutadiene; styrene and maleimide on polybutadiene; styrene andalkyl acrylates or methacrylates on polybutadiene; styrene andacrylonitrile on ethylene/propylene/diene terpolymers; styrene andacrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styreneand acrylonitrile on acrylate/butadiene copolymers, as well as mixturesthereof with the copolymers listed under 6), for example the copolymermixtures known as ABS, MBS, ASA or AES polymers.

8. Halogen-containing polymers such as polychloroprene, chlorinatedrubbers, chlorinated or sulfochlorinated polyethylene, copolymers ofethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers,especially polymers of halogen-containing vinyl compounds, for examplepolyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride,polyvinylidene fluoride, as well as copolymers thereof such as vinylchloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidenechloride/vinyl acetate copolymers.

9. Polymers derived from α,β-unsaturated acids and derivatives thereofsuch as polyacrylates and polymethacrylates; polymethyl methacrylates,polyacrylamides and polyacrylonitriles, impact-modified with butylacrylate.

10. Copolymers of the monomers mentioned under 9) with each other orwith other unsaturated monomers, for example acrylonitrile/butadienecopolymers, acrylonitrile/alkyl acrylate copolymers,acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halidecopolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.

11. Polymers derived from unsaturated alcohols and amines or the acylderivatives or acetals thereof, for example polyvinyl alcohol, polyvinylacetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate,polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well astheir copolymers with olefins mentioned in 1) above.

12. Homopolymers and copolymers of cyclic ethers such as polyalkyleneglycols, polyethylene oxide, polypropylene oxide or copolymers thereofwith bisglycidyl ethers.

13. Polyacetals such as polyoxymethylene and those polyoxymethyleneswhich contain ethylene oxide as a comonomer; polyacetals modified withthermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulfides, and mixtures of polyphenyleneoxides with styrene polymers or polyamides.

15. Polyurethanes derived from hydroxyl-terminated polyethers,polyesters or polybutadienes on the one hand and aliphatic or aromaticpolyisocyanates on the other, as well as precursors thereof.

16. Polyamides and copolyamides derived from diamines and dicarboxylicacids and/or from aminocarboxylic acids or the corresponding lactams,for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12,4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides startingfrom m-xylene diamine and adipic acid; polyamides prepared fromhexamethylenediamine and isophthalic or/and terephthalic acid and withor without an elastomer as modifier, for examplepoly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenyleneisophthalamide; and also block copolymers of the aforementionedpolyamides with polyolefins, olefin copolymers, ionomers or chemicallybonded or grafted elastomers; or with polyethers, e.g. with polyethyleneglycol, polypropylene glycol or polytetramethylene glycol; as well aspolyamides or copolyamides modified with EPDM or ABS; and polyamidescondensed during processing (RIM polyamide systems).

17. Polyureas, polyimides, polyamide-imides and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and/or fromhydroxycarboxylic acids or the corresponding lactones, for examplepolyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates,as well as block copolyether esters derived from hydroxyl-terminatedpolyethers; and also polyesters modified with polycarbonates or MBS.

19. Polycarbonates and polyester carbonates.

20. Polysulfones, polyether sulfones and polyether ketones.

21. Crosslinked polymers derived from aldehydes on the one hand andphenols, ureas and melamines on the other hand, such asphenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins.

22. Drying and non-drying alkyd resins.

23. Unsaturated polyester resins derived from copolyesters of saturatedand unsaturated dicarboxylic acids with polyhydric alcohols and vinylcompounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

24. Crosslinkable acrylic resins derived from substituted acrylates, forexample epoxy acrylates, urethane acrylates or polyester acrylates.

25. Alkyd resins, polyester resins and acrylate resins crosslinked withmelamine resins, urea resins, polyisocyanates or epoxy resins.

26. Crosslinked epoxy resins derived from polyepoxides, for example frombisglycidyl ethers or from cycloaliphatic diepoxides.

27. Natural polymers such as cellulose, rubber, gelatin and chemicallymodified homologous derivatives thereof, for example cellulose acetates,cellulose propionates and cellulose butyrates, or the cellulose etherssuch as methyl cellulose; as well as rosins and their derivatives.

28. Blends of the aforementioned polymers (polyblends), for examplePP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS,PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR,PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 andcopolymers, PA/HDPE, PA/PP, PA/PPO.

29. Naturally occurring and synthetic organic materials which are puremonomeric compounds or mixtures of such compounds, for example mineraloils, animal and vegetable fats, oil and waxes, or oils, fats and waxesbased on synthetic esters (e.g. phthalates, adipates, phosphates ortrimellitates) and also mixtures of synthetic esters with mineral oilsin any weight ratios, typically those used as spinning compositions, aswell as aqueous emulsions of such materials.

30. Aqueous emulsions of natural or synthetic rubber, e.g. natural latexor latices of carboxylated styrene/butadiene copolymers.

31. Polysiloxanes such as the soft, hydrophilic polysiloxanes described,for example, in U.S. Pat. No. 4,259,467; and the hardpolyorganosiloxanes described, for example, in U.S. Pat. No. 4,355,147.

32. Polyketimines in combination with unsaturated acrylicpolyacetoacetate resins or with unsaturated acrylic resins. Theunsaturated acrylic resins include the urethane acrylates, polyetheracrylates, vinyl or acryl copolymers with pendant unsaturated groups andthe acrylated melamines. The polyketimines are prepared from polyaminesand ketones in the presence of an acid catalyst.

33. Radiation curable compositions containing ethylenically unsaturatedmonomers or oligomers and a polyunsaturated aliphatic oligomer.

34. Epoxymelamine resins such as light-stable epoxy resins crosslinkedby an epoxy functional coetherified high solids melamine resin such asLSE-4103 (Monsanto).

In general, the compounds of the present invention are employed in fromabout 0.01 to about 5% by weight of the stabilized composition, althoughthis will vary with the particular substrate and application. Anadvantageous range is from about 0.05 to about 3%, and especially 0.05to about 1%.

The stabilizers of the instant invention may readily be incorporatedinto the organic polymers by conventional techniques, at any convenientstage prior to the manufacture of shaped articles therefrom. Forexample, the stabilizer may be mixed with the polymer in dry powderform, or a suspension or emulsion of the stabilizer may be mixed with asolution, suspension, or emulsion of the polymer. The resultingstabilized polymer compositions of the invention may optionally alsocontain from about 0.01 to about 5%, preferably from about 0.025 toabout 2%, and especially from about 0.1 to about 1% by weight of variousconventional additives, such as the materials listed below, or mixturesthereof.

1. Antioxidants

1.1. Alkylated monophenols for example,

2,6-di-tert-butyl-4-methylphenol

2-tert-butyl-4,6-dimethylphenol

2,6-di-tert-butyl4-ethylphenol

2,6-di-tert-butyl-4-n-butylphenol

2,6-di-tert-butyl-4-i-butylphenol

2,6-di-cyclopentyl-4-methylphenol

2-(α-methylcyclohexyl)-4,6-dimethylphenol

2,6-di-octadecyl-4-methylphenol

2,4,6-tri-cyclohexylphenol

2,6-di-tert-butyl-4-methoxymethylphenol

1.2. Alkylated hydroquinones, for example,

2,6-di-tert-butyl-4-methoxyphenol

2,5-di-tert-butyl-hydroquinone

2,5-di-tert-amyl-hydroquinone

2,6-diphenyl-4-octadecyloxyphenol

1.3. Hydroxylated thiodiphenyl ethers, for example,

2,2′-thio-bis-(6-tert-butyl-4-methylphenol)

2,2′-thio-bis-(4-octylphenol)

4,4′-thio-bis-(6-tert-butyl-3-methylphenol)

4,4′-thio-bis-(6-tert-butyl-2-methylphenol)

1.4. Alkylidene-bisphenols, for example,

2,2′-methylene-bis-(6-tert-butyl-4-methylphenol)

2,2′-methylene-bis-(6-tert-butyl-4-ethylphenol)

2,2′-methylene-bis-[4-methyl-6-(α-methylcyclohexyl)-phenol]

2,2′-methylene-bis-(4-methyl-6-cyclohexylphenol)

2,2′-methylene-bis-(6-nonyl-4-methylphenol)

2,2′-methylene-bis-[6-(α-methylbenzyl)-4-nonylphenol]

2,2′-methylene-bis-[6-(α,α-dimethylbenzyl)-4-nonylphenol]

2,2′-methylene-bis-(4,6-di-tert-butylphenol)

2,2′-ethylidene-bis-(4,6-di-tert-butylphenol)

2,2′-ethylidene-bis-(6-tert-butyl-isobutylphenol)

44,′-methylene-bis-(2,6-di-tert-butylphenol)

4,4′-methylene-bis-(6-tert-butyl-2-methylphenol)

1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane

2,6-di-(3-tert-butyl-5-methyl-2-hydroxybenzyl)4-methylphenol

1,1,3-tris-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane

1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane

ethyleneglycol bis-[3,3-bis-(3′-tert-butyl-4′-hydroxyphenyl)-butyrate]

di-(3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene

di-[2-(3′-tert-butyl-2′-hydroxy-5′-methyl-benzyl)-6-tert-butyl-4-methylphenyl]terephthalate.

1.5. Benzyl compounds, for example,

1,3,5-tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene

di-(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide

3,5-di-tert-butyl-4-hydroxybenzyl-mercapto-acetic acid isooctyl ester

bis-(4tert-butyl-3-hydroxy-2,6dimethylbenzyl)dithiol terephthalate

1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate

1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate

3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid dioctadecyl ester

3,5di-tert-butyl-4-hydroxybenzyl-phosphoric acid monoethyl ester,calcium-salt

1.6. Acylaminophenols, for example,

4-hydroxy-lauric acid anilide

4-hydroxy-stearic acid anilide

2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazine

octyl-N-(3,5di-tert-butyl-4-hydroxyphenyl)-carbamate

1.7. Esters of β-(3.5-di-tert-butyl-4-hydroxyphenyl)-propionic acid withmonohydric or polyhydric alcohols, for example,

methanol diethylene glycol octadecanol triethylene glycol 1,6-hexanediolpentaerythritol neopentyl glycol tris-hydroxyethyl isocyanuratethiodiethylene glycol di-hydroxyethyl oxalic acid diamidetriethanolamine triisopropanolamine

1.8. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acidwith monohydric or polyhydric alcohols, for example,

methanol diethylene glycol octadecanol triethylene glycol 1,6-hexanediolpentaerythritol neopentyl glycol tris-hydroxyethyl isocyanuratethiodiethylene glycol di-hydroxyethyl oxalic acid diamidetriethanolamine triisopropanolamine

1.9. Amides of β-(3.5-di-tert-butyl-4-hydroxyphenyl)-propionic acid forexample,

N,N′-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexamethylenediamine

N,N′-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-trimethylenediamine

N,N′-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine

1.10 Diarylamines, for example,

diphenylamine, N-phenyl-1-naphthylamine,N-(4-tert-octylphenyl)-1-naphthylamine,4,4′-di-tert-octyl-diphenylamine, reaction product ofN-phenylbenzylamine and 2,4,4-trimethylpentene, reaction product ofdiphenylamine and 2,4,4-trimethylpentene, reaction product ofN-phenyl-1-naphthylamine and 2,4,4-trimethylpentene.

2. UV absorbers and light stabilizers

2.1. 2-(2′-Hydroxyphenyl)-benzotriazoles, for example, the 5′-methyl-,3′,5′-di-tert-butyl-, 5′-tert-butyl-, 5′-(1,1,3,3-tetramethylbutyl)-,5-chloro-3′,5′-di-tert-butyl-, 5-chloro-3′-tert-butyl-5′-methyl-,3′-sec-butyl-5′-tert-butyl-, 4′-octoxy, 3′,5′-di-tert-amyl-,3′,5′-bis-(α,α-dimethylbenzyl),3′-tert-butyl-5′-(2-(omega-hydroxy-octa-(ethyleneoxy)carbonyl-ethyl)-,3′-dodecyl-5′-methyl-,3′-tert-butyl-5′-(2-octyloxycarbonyl)ethyl-, dodecylated-5′-methylderivatives; and2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole.

2.2. 2-Hydroxy-benzophenones, for example, the 4-hydroxy-, 4-methoxy-,4-octoxy, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy, 4,2′,4′-trihydroxy-and 2′-hydroxy-4,4′-dimethoxy derivatives.

2.3. Esters of optionally substituted benzoic acids for example, phenylsalicylate, 4-tert-butylphenyl salicylate, octylphenyl salicylate,dibenzoylresorcinol, bis-(4-tert-butylbenzoyl)-resorcinol,benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid2,4-di-tert-butylphenyl ester and 3,5-di-tert-butyl-4-hydroxybenzoicacid hexadecyl ester.

2.4. Acrylates, for example, α-cyano-β,β-diphenylacrylic acid ethylester or isooctyl ester, α-carbomethoxy-cinnamic acid methyl ester,α-cyano-β-methyl-p-methoxy-cinnamic acid methyl ester or butyl ester,α-carbomethoxy-p-methoxy-cinnamic acid methyl ester,N-(β-carbomethoxy-β-cyanovinyl)-2-methyl-indoline.

2.5. Nickel compounds, for example, nickel complexes of2,2′-thio-bis-[4-(1,1,3,3-tetramethylbutyl)-phenol], such as the 1:1 or1:2 complex, optionally with additional ligands such as n-butylamine,triethanolamine or N-cyclohexyl-diethanolamine, nickeldibutyldithiocarbamate, nickel salts of4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, suchas of the methyl, ethyl or butyl ester, nickel complexes of ketoximessuch as of 2-hydroxy-4-methyl-phenyl undecyl ketoxime, nickel complexesof 1-phenyl-4-lauroyl-5-hydroxy-pyrazole, optionally with additionalligands.

2.6. Sterically hindered amines, for examplebis-(2,2,6,6-tetramethylpiperidyl) sebacate,bis-(1,2,2,6,6-pentamethylpiperidyl) sebacate,n-butyl-3,5-di-tert.butyl-4-hydroxybenzyl malonic acidbis-(1,2,2,6,6-pentanemethylpiperidyl)ester, condensation product of1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, condensation product ofN,N′-(2,2,6,6-tetramethylpiperidyl)-hexamethylenediamine and4-tert-octylamino-2,6-dichloro-s-triazine,tris-(2,2,6,6-tetramethylpiperidyl)-nitrilotriacetate,tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate,1,1′(1,2-ethanediyl)-bis-(3,3,5,5-tetramethylpiperazinone),bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate.2-(2-hydroxyethylamino)-4,6-bis{N-[1-(cyclohexyloxy)-2,2,6,6-tetramethylpiperidin-4-yl]-butylamino-s-triazine,oligomer ofN-{[2-(N-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazin-4-yl}-N,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)-1,6-hexanediamineterminated with 2,4-bis(dibutylamino)-s-triazin-6-yl,N,N′,N″-tris{2,4-bis[N-(1,2,2,6,6-pentamethylpiperidin-4-yl)butyl-amino]-s-triazin-6-yl}3,3′-ethylenediiminodipropylamine,N,N′,N′″-tris{2,4-bis[N-(1,2,2,6,6-pentamethylpiperidin-4-yl)butylamino]-s-triazin-6-yl}3,3′-ethylenediiminodipropylamineandN,N′,N″,N′″-tetrakis{2,4-bis[N-(1,2,2,6,6-pentamethylpiperidin-4-yl)butylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamine;N,N′,N″-tris{2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamine,N,N′,N′″-tris{2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamineandN,N′,N″,N′″-tetrakis{2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazin-6-yl}3,3′-ethylenediiminodipropylamine.

2.7. Oxalic acid diamides, for example, 4,4′-di-octyloxy-oxanilide,2,2′-di-octyloxy-5,5′-di-tert-butyl-oxanilide,2,2′-di-dodecyloxy-5,5′-di-tert-butyl-oxanilide,2-ethoxy-2′-ethyl-oxanilide, N,N′-bis (3-dimethylaminopropyl)-oxalamide,2-ethoxy-5-tert-butyl-2′-ethyloxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butyloxanilide and mixtures of ortho- andpara-methoxy- as well as of o- and p-ethoxy-disubstituted oxanilides.

2.8. Hydroxyphenyl-s-triazines, for example2,6-bis-(2,4-dimethylphenyl)-4-(2-hydroxy-4-octyloxyphenyl)-s-triazine;2,6-bis-(2,4-dimethylphenyl)-4-(2,4-dihydroxyphenyl)-s-triazine;2,4-bis(2 ,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(2,4-dimethylphenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)-phenyl]-6-(4-bromophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-acetoxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine,2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine.

3. Metal deactivators, for example, N,N′-diphenyloxalic acid diamide,N-salicylal-N′-salicyloylhydrazine, N,N′-bis-salicyloylhydrazine,N,N′-bis-(3,5di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine,3-salicyloylamino-1,2,4-triazole, bis-benzylidene-oxalic aciddihydrazide.

4. Phosphites and phosphonites, for example, triphenyl phosphite,diphenylalkyl phosphites, phenyldialkyl phosphites, tri-(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite,di-stearyl-pentaerythritol diphosphite, tris-(2,4-di-tert-butylphenyl)phosphite, di-iso-decylpentaerythritol diphosphite,di-(2,4,6-tri-tert-butylphenyl)-pentaerythritol diphosphite,di-(2,4-di-tert-butyl-6-methylphenyl)-pentaerythritol diphosphite,di-(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,tristearyl-sorbitol triphosphite, tetrakis-(2,4-di-tert-butylphenyl)4,4′-diphenylylenediphosphonite.

5. Compounds which destroy peroxide, for example, esters ofβ-thiodipropionic acid, for example the lauryl, stearyl, myristyl ortridecyl esters, mercapto-benzimidazole or the zinc salt of2-mercaptobenzimidazole, zinc dibutyl-dithiocarbamate, dioctadecyldisulfide, pentaerythritol tetrakis-(β-dodecylmercapto)-propionate.

6. Hydroxylamines, for example, N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxyl-amine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.

7. Nitrones, for example, N-benzyl-alpha-phenyl nitrone,N-ethyl-alpha-methyl nitrone, N-octyl-alpha-heptyl nitrone,N-lauryl-alpha-undecyl nitrone, N-tetradecyl-alpha-tridecyl nitrone,N-hexadecyl-alpha-pentadecyl nitrone,N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-alpha-heptadecylnitrone, N-octadecyl-alpha-pentadecylnitrone,N-heptadecyl-alpha-heptadecyl nitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N,N-dialkylhydroxylamine derived fromhydrogenated tallow amine.

8. Polyamide stabilizers, for example copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese.

9. Basic co-stabilizers, for example, melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids for example Castearate, Zn stearate, Mg stearate, Na ricinoleate and K palmitate,antimony pyrocatecholate or zinc pyrocatecholate.

10. Nucleating agents, for example, 4-tert-butyl-benzoic acid, adipicacid, diphenylacetic acid.

11. Fillers and reinforcing agents, for example, calcium carbonate,silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate,metal oxides and hydroxides, carbon black, graphite.

12. Other additives, for example, plasticizers, lubricants, emulsifiers,pigments, optical brighteners, flameproofing agents, anti-static agents,blowing agents and thiosynergists such as dilauryl thiodipropionate ordistearyl thiodipropionate.

13. Benzofuranones and indolinones, for example those disclosed in U.S.Pat. No. 4,325,863, U.S. Pat. No. 4,338,244 or U.S. Pat. No. 5,175,312,or 3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one.

The co-stabilizers, with the exception of the benzofuranones listedunder 11, are added for example in concentrations of 0.01 to 10%,relative to the total weight of the material to be stabilized.

Further preferred compositions comprise, in addition to components (a)and (b) further additives, in particular phenolic antioxidants, lightstabilizers or processing stabilizers.

Particularly preferred additives are phenolic antioxidants (item 1 ofthe list), sterically hindered amines (item 2.6 of the list), phosphitesand phosphonites (item 4 of the list) and peroxide-destroying compounds(item 5.) of the list.

Additional additives (stabilizers) which are also particularly preferredare benzofuran-2-ones, such as described, for example, in U.S. Pat. No.4,325,863, U.S. Pat. No. 4,338,244 or U.S. Pat. No. 5,175,312.

The phenolic antioxidant of particular interest is selected from thegroup consisting of n-octadecyl3,5-di-tert-butyl-4-hydroxyhydrocinnamate, neopentanetetrayltetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinammate), di-n-octadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,3,6-dioxaoctamethylenebis(3-methyl-5-tert-butyl-4-hydroxyhydrocinnamate),2,6-di-tert-butyl-p-cresol,2,2′-ethylidene-bis(4,6-di-tert-butylphenol),1,3,5-tris(2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl)isocynurate,1,1,3,-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane,1,3,5-tris-[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)ethyl]isocyanurate, 3,5-di-(3,5-di-tert-butyl-4-hydroxybenzyl)mesitol, hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),1-(3,5-di-tert-butyl-4-hydroxyanilino)-3,5-di(octylthio)-s-triazine,N,N′-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide),calcium bis(ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate),ethylene bis[3,3-di(3-tert-butyl-4-hydroxyphenyl)butyrate], octyl3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate,bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazide, andN,N′-bis[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)-ethyl]-oxamide.

A most preferred phenolic antioxidant is neopentanetetrayltetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), n-octadecyl3,5-di-tert-butyl-4-hydroxyhydrocinnamate,1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,2,6-di-tert-butyl-p-cresol or2,2′-ethylidene-bis(4,6-di-tert-butylphenol).

The hindered amine compound of particular interest is selected from thegroup consisting of bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate,bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate,di(1,2,2,6,6-pentamethylpiperidin4-yl)(3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate,4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triaza-spiro[4.5]decane-2,4-dio ne,tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate,1,2-bis(2,2,6,6-tetramethyl-3-oxopiperazin-4-yl)ethane,2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxodispiro[5.1.11.2]heneicosane, polycondensation product of2,4-dichloro-6-tert-octylamino-s-triazine and4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),polycondensation product of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, polycondensation product of4,4′-hexamethylenebis-(amino-2,2,6,6-tetramethylpiperidine) and1,2-dibromoethane, tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)1,2,3,4-butanetetracarboxylate,tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl)1,2,3,4-butanetetracarboxylate, polycondensation product of2,4dichloro-6-morpholino-s-triazine and4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),N,N′,N″,N′″-tetrakis[(4,6-bis(butyl-1,2,2,6,6-pentamethylpiperidin-4-yl)-amino-s-triazin-2-yl]-1,10-diamino-4,7-diazadecane,polycondensation product of 2,4-dichloro-6-morpholino-s-triazine and4,4′-hexamethylenebis(amino-1,2,2,6,6-pentamethylpiperidine), mixed[2,2,6,6-tetramethylpiperidin-4-yl/β,β,β′,β′-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]-undecane)diethyl] 1,2,3,4-butanetetracarboxylate, mixed[1,2,2,6,6-pentamethylpiperidin-4-yl/β,β,β′,β′-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]undecane)diethyl]1,2,3,4-butanetetracarboxylate, octamethylenebis(2,2,6,6-tetramethylpiperidin-4-carboxylate),4,4′-ethylenebis(2,2,6,6-tetramethylpiperazin-3-one),N-2,2,6,6-tetramethylpiperidin-4-yl-n-dodecylsuccinimide,N-1,2,2,6,6-pentamethylpiperidin-4-yl-n-dodecylsuccinimide,N-1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl-n-dodecylsuccinimide,1-acetyl3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,di-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate,1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine,poly-{[6-tert-octylamino-s-triazin-2,4-diyl][2-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin4-yl)imino-hexamethylene-[4-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino],2,4,6-tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-n-butylamino]-s-triazine,

2-(2-hydroxyethylamino)-4,6-bis{N-[1-(cyclohexyloxy)-2,2,6,6-tetramethylpiperidin-4-yl]-butylamino-s-triazine,oligomer ofN-{[2-(N-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazin-4-yl}-N,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)-1,6-hexanediamineterminated with 2,4-bis(dibutylamino)-s-triazin-6-yl,N,N′,N″-tris{2,4-bis[N-(1,2,2,6,6-pentamethylpiperidin-4-yl)butylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamine,N,N′,N′″-tris{2,4-bis[N-(1,2,2,6,6-pentamethylpiperidin-4-yl)butylamino]-s-triazin-6-yl}3,3′-ethylenediiminodipropylamineandN,N′,N″,N′″-tetrakis{2,4-bis[N-(1,2,2,6,6-pentamethylpiperidin-4-yl)butylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamine;N,N′,N″-tris{2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-y)butylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamine,N,N′,N′″-tris{2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazin-6-yl)3,3′-ethylenediiminodipropylamine,N,N′,N″,N′″-tetrakis{2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazin-6-yl)3,3′-ethylenediiminodipropylamine,oligomer ofN-{2-[(1-propoxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazin-4-yl)N,N′-bis(1-propoxy-2,2,6,6-tetramethylpiperidin-4-yl)-1,6-hexanediamine terminatedwith 2,4-bis(dibutylamino)-s-triazin-6-yl, or the condensation productof 2-morpholino-4,6-dichloro-s-triazine withN,N′-bis(1,2,2,6,6-pentamethylpiperidin4-yl)-1,6-hexanediamine.

A most preferred hindered amine compound isbis(2,2,6,6-tetramethylpiperidin-4yl) sebacate,bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate,di(1,2,2,6,6-pentamethylpiperidin-4-yl)(3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate, the polycondensationproduct of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidineand succinic acid, the polycondensation product of2,4-dichloro-6-tert-octylamino-s-triazine and4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),N,N′,N″,N′″-tetrakis[(4,6-bis(butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino)-s-triazine-2-yl]-1,10-diamino-4,7-diazadecane.di-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate,1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine,poly-{[6-tert-octylamino-s-triazin-2,4-diyl][2-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino-hexamethylene-[4-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino],or2,4,6-tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-n-butylamino]-s-triazine.

The instant composition can additionally contain another UV absorberselected from the group consisting of the s-triazines, the oxanilides,the hydroxybenzophenones, benzoates and the α-cyanoacrylates.

Particularly, the instant composition may additionally contain aneffective stabilizing amount of at least one other2-hydroxyphenyl-2H-benzotriazole; another tris-aryl-s-triazine; orhindered amine or mixtures thereof.

Preferably, the 2-hydroxyphenyl-2H-benzotriazole is selected from thegroup consisting of

2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole;

2-[2-hydroxy-3,5-di(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole;

2-[2-hydroxy-3-(α,α-dimethylbenzyl)-5-tert-octylphenyl]-2H-benzotriazole;

2-[2-hydroxy-3-tert-butyl-5-[2-(omega-hydroxy-octa(ethyleneoxy)carbonyl)ethyl]phenyl}-2H-benzotriazole;and

2-{2-hydroxy-3-tert-butyl-5-[2-(octyloxy)carbonyl)ethyl]phenyl}2H-benzotriazole.

Preferably the 2-hydroxyphenyl-2H-benzotriazole may also be selectedfrom the group consisting of

(a)5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole;

(b) 5-trifluoromethyl-2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole;

(c)5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole;

(d)2,2′-methylene-bis[6-(5-trifluoromethyl-2H-benzotriazol-2-yl)-4-tert-octylphenol];

(e)methylene-2-[4-tert-octyl-6-(2H-benzotriazol-2-yl)phenol]2′-[4-tert-octyl-6-(5-trifluoromethyl-2H-benzotriazol-2-yl)phenol];

(f)3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamicacid;

(g) methyl3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate;

(h) isooctyl3-(5trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate;

(i)5-trifluoromethyl-2-[2-hydroxy-5-(3-hydroxypropyl)phenyl]-2H-benzotriazole;

(j)5-trifluoromethyl-2-[2-hydroxy-5-(3-acryloyloxypropyl)phenyl]-2H-benzotriazole;

(k)5-trifluoromethyl-2-[2-hydroxy-5-(3-methacryloyloxypropyl)phenyl]-2H-benzotriazole;

(l)5-trifluoromethyl-2-[2-hydroxy-5-(3-acrylylaminopropyl)phenyl]-2H-benzotriazole;

(m)5-trifluoromethyl-2-[2-hydroxy-5-(3-methacrylylaminopropyl)phenyl]-2H-benzotriazole;

(n)5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-butylphenyl)-2H-benzotriazole;

(o)5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-nonylphenyl)-2H-benzotriazole;

(p)5-trifluoromethyl-2-[2-hydroxy-3-α-cumyl-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole;

(q)5-trifluoromethyl-2-[2-hydroxy-3-α-cumyl-5-(3-hydroxypropyl)phenyl]-2H-benzotriazole;

(r)5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole;

(s)5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;

(t)5-trifluoromethyl-2-(2-hydroxy-3-dodecyl-5-methylphenyl)-2H-benzotriazole;

(u)5-trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5-(3-hydroxypropyl)phenyl)-2H-benzotriazole;

(v)5-trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole;

(w)5-trifluoromethyl-2-[2-hydroxy-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole;

(x)5-trifluoromethyl-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole;

(y) 5-fluoro-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole;

(z) 5-butylsulfonyl-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole;

(aa)5-butylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;

(bb)5-butylsulfonyl-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole;and

(cc)5-phenylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole.

Preferably, the other tris-aryl-s-triazine is selected from the groupconsisting of

2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-s-triazine;

2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-s-triazine;

2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-do-/tri-decyloxy-2-hydroxypropoxy)-phenyl]-s-triazine;and

2-(2-hydroxyethylamino)-4,6-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-s-triazine.

The acrylic resin lacquers which can be stabilized against light,moisture and oxygen in accordance to the instant invention areconventional acrylic resin stoving lacquers or thermosetting resinsincluding acrylic/melamine systems which are described, for example, inH. Kittel's “Lehrbuch and Beschichtungen”, Vol. 1, Part 2 on pages 735and 742 (Berlin 1972), “Lackkunstharze” (1977) by H. Wagner and H. F.Sarx on pages 229-238, and in S. Paul's “Surface Coatings: Science andTechnology”, (1985).

The polyester lacquers which can be stabilized against the action oflight and moisture are conventional stoving lacquers described e.g. inH. Wagner and H. F. Sarx, op. cit., on pages 86-99.

The alkyd resin lacquers which can be stabilized against the action oflight and moisture in accordance with the instant invention are theconventional stoving lacquers which are used in particular for coatingautomobiles (automobile finishing lacquers), for example lacquers basedon alkyd/melamine resins and alkyd/acrylic/melamine resins (see H.Wagner and H. F. Sarx, “Lackkunstharze” (1977), pages 99-123). Othercrosslinking agents include glycoluril resins, blocked or unblockedisocyanates or epoxy resins. Other lacquers which can be stabilizedinclude those with crosslinkable functionalities such as carbamate andsiloxane.

The lacquers stabilized in accordance with the invention are suitableboth for metal finish coatings and solid shade finishes, especially inthe case of retouching finishes, as well as various coil coatingapplications. The lacquers stabilized in accordance with the inventionare preferably applied in the conventional manner by two methods, eitherby the single-coat method or by the two-coat method. In the lattermethod, the pigment-containing base coat is applied first and then acovering coat of clear lacquer over it.

Although major emphasis in this application is directed toacid-catalyzed baked finishes, it is also to be noted that the compoundsof the present invention are applicable for use in non-acid catalyzedthermoset resins such as epoxy, epoxy-polyester, vinyl, alkyd, acrylicand polyester resins, optionally modified with silicon, isocyanates orisocyanurates. The epoxy and epoxy-polyester resins are crosslinked withconventional crosslinkers such as acids, acid anhydrides, amines and thelike. Correspondingly, the epoxide may be utilized as the crosslinkingagent for various acrylic or polyester resin systems that have beenmodified by the presence of reactive groups on the backbone structure.

The amount of instant stabilizer compound used is 0.1 to 5% by weight,based on the solvent-free binder, preferably 0.5 to 2% by weight. Thebinders can be dissolved or dispersed in customary organic solvents orin water or can be solvent-free.

When used in two-coat finishes, the compounds of the instant inventioncan be incorporated in the clear coat or both in the clear coat and inthe pigmented base coat.

To attain maximum light stability, the concurrent use of otherconventional light stabilizers can be advantageous. Examples are UVabsorbers of the benzophenone, benzotriazole, acrylic acid derivatives,oxalanilide, aryl-s-triazine or metal-containing types (e.g. organicnickel compounds). In two-coat systems, these additional lightstabilizers can be added to the clear coat and/or the pigmented basecoat.

If such combinations of stabilizers are used, the sum of all lightstabilizers is 0.2 to 20% by weight, preferably 0.5 to 5% by weight,based on the film-forming resin.

When water-soluble, water miscible or water dispersible coating aredesired ammonium salts of acid groups present in the resin are formed.Powder coating composition can be prepared by reacting glycidylmethacrylate with selected alcohol components.

It is also contemplated that the instant compounds would find particularvalue when used with water-soluble inks and related polar orientedutilities where the presence of the OH moiety would provide for bettercompatibility and properties related to such aqueous environments.

The instant compounds are also useful in the stabilization of acidcatalyzed thermoset resins which are disclosed in U.S. Pat. No.5,112,890, the relevant parts of which are incorporated herein byreference.

These resins are used in baked enamels or stoving lacquers. Hinderedamine light stabilizaers are well known to be effective in stabilizing ahost of organic substrates including polymers from the deleteriouseffects of oxygen and light. Such hindered amine light stabilizers havebeen used in the stabilization of hot-crosslinkable alkyd or acrylicmetallic stoving lacquers (see U.S. Pat. No. 4,426,472) and instabilizing acid-catalyzed stoving lacquers based on hot-crosslinkableacrylic polyester or alkyl resins (see U.S. Pat. Nos. 4,344,876 and4,426,471). None of the hindered amine light stabilizers of thesepatents possess structures having an O-substituted hydroxyl groupsubstituted directly on the N-atom of the hindered amine. The instantcompounds have such substitution and additionally are even less basicthan the NOR compounds described in U.S. Pat. No. 5,112,890 as is seenin instant working Example 114.

In their industrial uses, enamels with high solids content based oncrosslinkable acrylic, polyester, urethane or alkyd resins are curedwith an additional acid catalyst. Light stabilizers containing a basicnitrogen group are generally less than satisfactory in this application.Formation of a salt between the acid catalyst and the light stabilizerleads to incompatibility or insolubility and recipitation of the saltand to a reduced level of cure and to reduced light protective actionand poor resistance to moisture.

The acid catalyzed thermoset enamels must be stabilized in order tofunction acceptably in end-use applications. The stabilizers used arehindered amines, preferably those substituted on the N-atom by an inertblocking group in order to prevent precipitation of the basic amine withthe acid catalyst with a concomitant retardation in cure, optionally incombination with UV absorbers as described above.

The stabilizers are needed to impart greater retention of durability tothe cured enamels (as measured by 20° gloss, distinction of image,cracking or chalking); the stabilizers must not retard cure (normal bakefor auto finishes at 121° C.; and low bake repair at 82° C.) as measuredby hardness, adhesion, solvent resistance and humidity resistance; theenamel should not yellow on curing and further color change on exposureto light should be minimized; the stabilizers should be soluble in theorganic solvents normally used in coating applications, such as methylamyl ketone, xylene, n-hexyl acetate, alcohol and the like.

The instant hindered amine light stabilizers on the N-atom by anO-substituted moiety containing a free hydroxyl group fulfill each ofthese requirements and provide alone or in combination with a UVabsorber outstanding light stabilization protection to the cured acidcatalyzed thermoset enamels.

The instant invention also pertains to resin systems capable of beingfully cured under ambient conditions. For example, applicable resinsinclude alkyd, acrylic, polyester and epoxide resins as described in S.Paul's “Surface Coatings: Science and Technology” (1985), pages 70-310.Various acrylic and modified acrylic resins are described in H. Kittel's“Lehrbuch der Lacke unde Beschichtungen”, Vol. 1, Part 2, on pages 735and 742 (Berlin 1972), and in “Lackkunstharze” (1977) by H. Wagner andH. F. Sarx, op. cit, on pages 229-238. Typical crosslinkable polyesterresins which can be stabilized against the action of light and moistureare described e.g. in H. Wagner and H. F. Sarx, op. cit., on pages86-99. The unmodified and modified alkyd resins which can be stabilizedare conventional resins which are used in trade sales, maintenance andautomotive refinish coatings. For example, such coatings are based onalkyd resins, alkyd/acrylic resins and alkyd/silicon reins (see H.Wagner and H. F. Sarx, op. cit., pages 99-123) optionally crosslinked byisocyanates or epoxy resins.

In addition various acrylic lacquer coating compositions are disclosedin U.S. Pat. No. 4,162,249. Other acrylic/alkyd resins withpolyisocyanate additives are disclosed in U.S. Pat. No. 4,471,083; andacrylic resins containing either pendant amino ester groups or glycidylgroups are described in U.S. Pat. No. 4,525,521.

The ambient cured coatings stabilized by the instant compounds aresuitable both for metal finish coatings and solid shade finishes,especially in the case of retouching finishes. The lacquers stabilizedby the instant compounds are preferably applied in a conventional mannerby two methods, either by the single-coat method or by the two-coatmethod. In the latter method, the pigment-containing base coat isapplied first and a covering coat of clear lacquer applied over it. Whenused in two-coat finishes, the instant hindered amine compound can beincorporated in the clear coat or both in the clear coat and in thepigmented base coat.

The instant invention also pertains to abrasion-resistant coatingcompositions suitable for coating over polycarbonates. Such coatings asdescribed in U.S. Pat. No. 5,214,085 comprise a silyl acrylate, aqueouscolloidal silica, a photoinitiator and optionally a polyfunctionalacrylate as well as UV absorbers. Such coatings provide resistance afterprolonged outdoor exposure to sunlight, moisture, thermal cyclingcausing yellowing, delamination and formation of microcracks anddecreasing transparency.

Related hindered amine stabilizers have been utilized individually andin combination with UV absorbers to improve the performancecharacteristics of ambient cured coating systems. Notwithstanding suchimprovements, there still exists a need to further retard thephotooxidation and photodegradation of such ambient cured systems andthereby provide increased effectiveness by maintaining the physicalintegrity of the coatings. Such effectiveness can be manifested byprevention of embrittlement, cracking, corrosion, erosion, loss ofgloss, chalking and yellowing of the coating.

It has now been determined that the aforementioned improvements can beachieved by substitution of the N-atom of the hindered amines with an—OR moiety and by the utilization of such derivatives in ambient curedcoating systems as is taught in U.S. Pat. No. 5,124,378, the relevantparts of which are incorporated herein by reference. The instantcompounds are even less basic than the compounds of U.S. Pat. No.5,124,378 and are particularly well suited for this task. In particular,the physical integrity of the coatings is maintained to a higher degreewith significant reduction in loss of gloss and in yellowing.Accordingly, the instant invention relates to the use of the instant NORcompounds, where the R moiety is further substituted by a hydroxylgroup, optionally together with further stabilizers, for stabilizingambient cured coatings based on alkyd resins; thermoset acrylic resins;acrylic alkyds; acrylic alkyd or polyester resins optionally modifiedwith silicon, isocyanates, isocyanurates, ketimines or oxazolidines; andepoxide resins crosslinked with carboxylic acids, anhydrides, polyaminesor mercaptans; and acrylic and polyester resin systems modified withreactive groups in the backbone thereof and crosslinked with epoxides;against the degradative effects of light, moisture and oxygen.

The instant invention also relates to electrodeposited coatings appliedto metal substrates where various top coats may be applied thereover.The inclusion of the instant compounds in the E-coat providesdelamination resistance to said E-coats. The primary resins in saidE-coats are acrylic or epoxy resins. These E-coats are described inEuropean patent application EP 0 576 943 A1.

The instant invention also pertains to UV-cured coating systems usingunsaturated acrylic resins, polyurethane acrylates, epoxy acrylates,polyester acrylates, unsaturated polyester/styrene resins and silylacrylates.

Synthesis of Compounds

The instant compounds may be prepared by the reaction of tributyltinhydride and a halogen substituted alcohol to produce carbon centeredradicals that are trapped by nitroxyl compounds.

The instant compounds may also be prepared by coupling an N-oxylhindered amine with a carbon centered radical generated by thephotochemical or thermal decomposition of a perester or dialkyl peroxidein the presence of an alcohol. The bridge compounds described above canbe formed when two nitroxyl radicals couple with the same solventmolecule, especially when the amount of solvent is reduced.

The preferred method of preparation of the instant compounds is to reactan N-oxyl hindered amine with a carbon centered radical generated bymixing an aqueous or alcoholic solution of a metal ion such as Fe²⁺,Fe³⁺, Cu²⁺ or Cu⁺ and a peroxide such as tert-butyl hydroperoxide orhydrogen peroxide in the presence of an alcohol solvent at a temperatureof 20-80° C. Especially effective is the combination of ferrouschloride, ferric chloride or ferrous sulfate, particularly ferrouschloride, or ferric chloride, and hydrogen peroxide. Water may be addedto the alcohol at the beginning of the reaction to improve solubility ofthe metal salt or to dissolve an alcohol which is solid at the reactiontemperature. A ligand such as 2,2′-dipyridyl, 2,2′:6′,2″-terpyridyl, maybe added to the reaction mixture. Two nitroxyl radicals can sometimescouple with the same solvent molecule to produce bridged compoundsdescribed in some formulas listed earlier. The formation of bridgecompounds is more favored when the amount of solvent is reduced.

Some of the instant hydroxy-substituted N-alkoxy compounds may bereacted with monofunctional or difunctional esters, acids or acidchlorides or isocyanates to form polymeric ester or urethanederivatives.

The following examples are for illustrative purposes only and are not tobe construed to limit the instant invention in any manner whatsoever.

EXAMPLE 1 Reaction of 1-Oxyl-2,2,6,6-tetramethylpiperidin-4-one withCyclohexanol

A solution of 55 g (0.49 mol) of 30% aqueous hydrogen peroxide is addeddropwise over a 4.25 hour period to a mixture of 23.5 g (0.14 mol) of1-oxyl-2,2,6,6-tetramethyl-piperidin-4-one and 4.0 g (0.020 mol) offerrous chloride tetrahydrate in 14 g (0.14 mol) of cyclohexanol and 150g of cyclohexane. The reaction temperature is maintained atapproximately 40° C. throughout the addition. The reaction mixture isstirred at 40° C. for three hours after the peroxide addition iscomplete. A second portion of 30% aqueous hydrogen peroxide (10 g, 0.09mol) is added and the reaction mixture is heated at 40° C. for sevenhours. After the mixture is cooled to room temperature, sodium sulfite(5 g) is added. The reaction temperature is carefully brought to 60° C.for one hour to decompose excess peroxide. Upon cooling, the organiclayer is separated, dried over anhydrous magnesium sulfate, andconcentrated to give 22.6 g of a brown oil. The oil is dissolved incyclohexane and passed through silica gel with cyclohexane and then 1:2(v/v) ethanol/cyclohexane to afford 16.5 g of a yellow oil.

Analysis by gass chromatography and mass spectrometry shows the productto be a mixture which contains at least four isomers of1-(hydroxycyclohexyloxy)-2,2,6,6-tetramethylpiperidin-4-one.

EXAMPLE 2Bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)]Sebacate

A solution of 73 g (0.64 mol) of 30% aqueous hydrogen peroxide is addeddropwise over a 3.5 hour period to a mixture of 30.0 g (0.059 mol) ofbis(1-oxyl-2,2,6,6-tetramethylpiperidin-yl) sebacate and 4.7 g (0.024mol) of ferrous chloride tetrahydrate in 150 g of tert-butyl alcohol and6 g of water. The reaction temperature is kept at approximately 40° C.throughout the peroxide addition. The reaction mixture is stirred at 40°C. for four hours after the addition is complete. The reaction mixtureis diluted with 150 g of ethyl acetate. A colution of 100 g of 20%aqueous sodium sulfite solution is added and the reaction mixture isstirred for 1.5 hours at 45-60° C. to decompose excess peroxide. Theaqueous layer is extracted with 100 g of ethyl acetate, and the combinedorganic layers are washed with 200 g of 5% sulfuric acid. Solvent isevaporated to obtain 39.4 g of a pale yellow liquid which is purified byflash chromatography on silica gel with a 4:1:5 part mixture (by volume)of ethyl acetate:isopropanol:hexane to afford 19.1 g (49% yield) of thetitle compound as a pale yellow oil.

¹Hnmr (CDCl₃): δ=3.65 ppm (4H, —NOCH₂—)

EXAMPLE 3 Reaction of Bis(1-oxyl-2,2,6,6-tetramethyl-piperidin-4-yl)Sebacate with Cyclohexanol

A solution of 70 g (0.62 mol) of 30% aqueous hydrogen peroxide is addeddropwise over 2.75 hours to a mixture of 32.4 g (0.063 mol) ofbis(1-oxyl-2,2,6,6-tetramethylpiperidin-yl) sebacate and 5.0 g (0.025mol) of ferrrous chloride tetrahydrate in 100 g of cyclohexanol. Thereaction temperature is maintained at 40-45° C. during the addition. Thereaction mixture is then stirred at 40° C. for five hours and duringthis time, fresh 50% aqueous hydrogen peroxide (5.0 g, 0.074 mol) isadded to the reaction mixture in two equal portions. The following day,the reaction mixture is heated to 40° C., another portion of 50% aqueoushydrogen peroxide (2.5 g, 0.037 mol) is added, and the mixture ismaintained at 40° C. for another five hours. A solution of 100 g of 20%aqueous sodium sulfite is added to the mixture and the reactiontemperature is maintained at 70° C. for 45 minutes to decompose excesshydrogen peroxide. The combined organic layers are concentrated to give151 g of crude product. Water is added, and residual cyclohexanol isremoved by steam distillation. The remaining 50 g of crude product ispurified by flash chromatography on silica gel with a 10:1:10 partmixture of ethyl acetate:ethanol:hexane to afford 32.9 g of an oil.

NMR analysis shows that the oil containsbis[1-(trans-2-hydroxycyclohexyloxy)-2,2,6,6-tetramethylpiperidin-4-yl]sebacate in addition to other structural isomers of said sebacatecompound.

EXAMPLE 4 Reaction of 4-Hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidinewith Cyclohexanol

A solution of 50 g (0.74 mol) of 50% aqueous hydrogen peroxide is addeddropwise over a 1.75 hour period to a mixture of 35.0 g (0.20 mol) of4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine and 10.0 gr (0.050 mol)of ferrous chloride tetrahydrate in 100 g of cyclohexanol. The reactiontemperature is maintained at approximately 40-45° C. throughout theaddition. After the peroxide addition is complete, the reaction mixtureis stirred at 40° C. for five hours. The mixture is cooled to roomtemperature and a solution of 100 g of 20% aqueous sodium sulfite isadded. The reaction mixture is carefully heated at 60° C. for one hourto decompose excess peroxide. After acetone is added to the organiclayer, the crude product mixture is filtered to remove solids and thefiltrate is concentrated. Water is added and residual cyclohexanol isremoved by steam distillation. The crude product is purified by flashchromatography on silica gel with 2:1 (v/v) hexane/ethyl acetate toafford 36.3 g of a yellow oil.

Analysis by mass spectrometry shows the oil to be a mixture of isomersof 1-(hydroxycyclohexyloxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine and1-(dihydroxycyclohexyloxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine.

EXAMPLE 5 Reaction of 2,4-Bis[N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)butylamino-6-chloro-s-triazine with Cyclohexanol

A solution of 30 g (0.44 mol) of 50% aqueous hydrogen peroxide is addedover a 2 hour period to a mixture of 39.4 g (0.070 mol) of2,4-bis[N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)butylamino-6-chloro-s-triazineand 7.0 g (0.035 mol) of ferrous chloride tetrahydrate in 150 g ofcyclohexanol at a temperature of 40-45° C. The reaction mixture isstirred at 40° C. for ten hours after the peroxide addition is complete,and during this time, another 19 g (0.28 mol) portion of 50% aqeuoushydrogen peroxide is added. Another portion of 50% aqueous hydrogenperoxide (25 g, 0.37 mol) is added while the reaction mixture is heatedat 50-65° C. for four hours. The reaction mixture is treated with asolution of 100 g of 20% aqueous sodium sulfite at 60° C. for one hourto decompose residual peroxide. The organic layer is concentrated to abrown oil which is extracted thrice with cyclohexane and once with ethylacetate. The combined extracts are concentrated to afford 43.4 g of ayellow solid.

EXAMPLE 6 2,4-Bis{N-[1-(trans-2-hydroxycyclohexyloxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino}-6-(2-hydroxyethyl)amino-s-triazine

The product obtained in Example 5 is reacted with ethanolamine andsodium hydroxide solution. The crude reaction mixture is duluted withethyl acetate and washed with water. The aqueous layer is extracted withethyl acetate, and the combined organic layers are concentrated. Theresidue is dissolved in ethyl acetate and cyclohexane is added. A brownoil is removed. The remaining solution is concentrated to give 13.7 g ofcrude product. The crude product is purified by flash chromatography onsilica gel with 2:1 (v/v) ethyl acetate/hexane and then 8:1 (v/v) ethylacetate/methanol to afford 6.4 g of a yellow oil. The oil is dissolvedin ethanol and treated with decolorizing carbon at 60° C. for one hour.Solids are removed by filtration and the solvent is evaporated to give6.5 g of an off-white solid, melting at 67-80° C.

NMR analysis shows the solid contains the title compound in addition toa mixture of hydroxycyclohexyloxy and dihydroxycyclohexyloxy structuralisomers.

EXAMPLE 7 Bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl] Adipate

Aqueous hydrogen peroxide is added to a mixture ofbis(1-oxyl-2,2,6,6-tetramethylpieridin-4-yl) adipate and ferrouschloride tetrahydrate in tert-butyl alcohol at 30-50° C. Excess peroxideis decomposed with aqeuous sodium sulfite solution. The organic layer isconcentrated and the crude product is purified by flash chromatographyon silica gel to afford the title compound.

EXAMPLE 8Bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]Glutarate

Aqueous hydrogen peroxide is added to a mixture ofbis(1-oxyl-2,2,6,6-tetramethylpieridin-4-yl) glutarate and ferrouschloride tetrahydrate in tert-butyl alcohol at 30-50° C. Excess peroxideis decomposed with aqeuous sodium sulfite solution. The organic layer isconcentrated and the crude product is purified by flash chromatographyon silica gel to afford the title compound.

EXAMPLE 9 Bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]Succinate

Aqueous hydrogen peroxide is added to a mixture ofbis(1-oxyl-2,2,6,6-tetramethylpieridin-4-yl) succinate and ferrouschloride tetrahydrate in tert-butyl alcohol at 30-50° C. Excess peroxideis decomposed with aqeuous sodium sulfite solution. The organic layer isconcentrated and the crude product is purified by flash chromatographyon silica gel to afford the title compound.

EXAMPLE 10 Bis[1-(2-hydroxy-1-phenethoxy)-2,2,6,6-tetramethylpiperidin-4-yl] Sebacate

Aqueous hydrogen peroxide is added to a mixture ofbis(1-oxyl-2,2,6,6-tetramethylpieridin-4-yl) sebacate and ferrouschloride tetrahydrate in phenethyl alcohol at 30-50° C. Excess peroxideis decomposed with aqeuous sodium sulfite solution. The organic layer isconcentrated and the crude product is purified by flash chromatographyon silica gel to afford the title compound.

EXAMPLE 112,4-Bis{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino}-6-chloro-s-triazine

A total of 40 g (0.59 mol) of 50% aqueous hydrogen peroxide is added intwo portions over five hours to a mixture of 43.2 g (0.076 mol) of2,4-bis[N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)butylamino-6-chloro-s-triazineand 7.0 g (0.035 mol) of ferrous chloride tetrahydrate in 150 g oftert-butyl alcohol and 15 g of water. Another portion of 50% aqueoushydrogen peroxide (3 g, 0.044 mol) is added to the reaction mixturewhile the temperature is maintained at 40-45° C. for 2.25 hours. Thereaction mixture is diluted with 100 g of ethyl acetate. A solution of100 g of 20% aqueous sodium sulfite is added and the reaction mixture isheated at 60° C. for one hour to decompose residual peroxide. Theaqueous layer is extracted with ethyl acetate, and the combined organiclayers are concentrated. The crude product is purified by flashchromatography on silica gel with 1:1 (v/v) hexane/ethyl acetate toafford 54.1 g of the title compound.

EXAMPLE 122,4-Bis{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino}-6-(2-hydroxyethyl)amino-s-triazine

The title compound is prepared by the reaction of the intermediateprepared in Example 11 with ethanolamine and sodium hydroxide. Theaqueous layer is removed, and the remaining layer is extracted withcyclohexane. Solvent is evaporated at reduced pressure, and the crudeproduct is purified by flash chromatography on silica gel with 1:2 (v/v)hexane/ethyl acetate to afford 4.1 g of the title compound as a whitesolid, melting at 110-120° C.

¹Hnmr (CDCl₃): δ=3.54 ppm (q,2H, NCH₂); 3.59 ppm (s,4H, NOCH₂).

EXAMPLE 13 Reaction of the Product of Example 11 withN,N′-Bis(3-aminopropyl)ethylenediamine

The product prepared in Example 11 is reacted withN,N′-bis(3-aminopropyl)ethylenediamine in a 3:1 molar ratio. The productmixture includesN,N′,N′″-tris{2,4-bis[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino]-s-triazin-6-yl)-3,3′-ethylenediiminodipropylamineandN,N′,N′″-tris{2,4-bis[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamine.

EXAMPLE 142,4-Bis{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino}-6-octylamino-s-triazine

The reaction of the compound prepared in Example 11 with excessoctylamine yields the title compound as an off-white glass melting at68-86° C.

EXAMPLE 15N,N′-Bis{4,6-bis{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino}-s-triazin-2-yl}1,6-diaminohexane

The title compound is prepared by the reaction of the compound preparedin Example 11 with hexamethylenediamine.

EXAMPLE 16A Reaction of 4-Hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidinewith tert-Butyl Alcohol

A solution of 50% aqueous hydrogen peroxide is added to a mixture of4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine and ferrous chloridetetrahydrate in tert-butyl alcohol at 30-60° C. Excess peroxide isdecomposed with aqeuous sodium sulfite. The organic layer isconcentrated and the crude product is purified by flash chromatographyon silica gel to afford a sample of4-hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine.

EXAMPLE 16B1-(2-Hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-ylMethacrylate

The title compound is prepared by reaction of the compound prepared inExample 16A with methyl methacrylate.

EXAMPLE 174-Allyloxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

The title compound is prepared by the reaction of the compound preparedin Example 16A with allyl bromide.

EXAMPLE 184-(2,3-Epoxypropoxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

The title compound is prepared by the reaction of the compound preparedin Example 16A with epichlorohydrin.

EXAMPLE 191-(2-Hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl3-{[[[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yloxy]carbonyl]-amino]methyl)}-3,5,5-trimethylcyclohexylcarbamate

The title compound is prepared by the reaction of the compound preparedin Example 16A with5-isocyanato-1-(isocyanatomethyl)-1,3,3-trimethylcyclohexane(=isophorone diisocyanate).

EXAMPLE 20Bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]1,6-Hexanedicarbamate

The title compound is prepared by the reaction of the compound preparedin Example 16A with hexamethylene diisocyanate.

EXAMPLE 211-(2-Hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl Acrylate

The title compound is prepared by the reaction of the compound preparedin Example 16A with methyl acrylate.

EXAMPLE 22

2,4,6-Tris{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino}-s-triazine

A solution of 40 g (0.35 mol) of 30% aqueous hydrogen peroxide is addedover 1.25 hours to a mixture of 11.7 g (0.011 mol) of2,4,6-tris[N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl]butylamino}-s-triazineand 3.0 g (0.015 mol) of ferrous chloride tetrahydrate in 100 g oftert-butyl alcohol and 9 g of water. The reaction temperature ismaintained at 60-65° C. during the peroxide addition. Two equal portions(2 g, 0.29 mol) of 50% aqueous hydrogen peroxide are added to thereaction mixture while the temperature is maintained at 60° C. for 9.5hours. After the reaction mixture is diluted with ethyl acetate andcooled to room temperature, a solution of 100 g of 20% aqueous sodiumsulfite is added. The reaction mixture is heated at 60° C. for one hourto decompose the excess peroxide. The aqueous layer is extracted withethyl acetate, and the combined organic layers are concentrated. Thecrude product is purified by flash chromatography on silica gel with 2:1(v/v) cyclohexane/ethyl acetate to afford a material which is trituratedwith 1:1 (v/v) cyclohexane/acetone to give 4.0 g of the title compoundas a white solid, melting at 172-176° C.

EXAMPLE 23A Reaction of 1-Oxyl-2,2,6,6-tetramethylpiperidin-4-one withtert-Butyl Alcohol

Aqueous hydrogen peroxide is added to a mixture of1-oxyl-2,2,6,6-tetramethylpiperidin-4-one and ferrous chloride intert-butyl alcohol at 30-60° C. Excess peroxide is decomposed withaqueous sodium sulfite. The organic layer is concentrated and theresidue is purified by flash chromatography to afford the desired1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-one.

EXAMPLE 23B4-Butylamino-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

A mixture of butylamine, the compound prepared in Example 23A and acatalytic amount of 5% platinum on carbon is hydrogenated at 3atmospheres using a Parr apparatus. The catalyst is removed byfiltration, and the solvent is evaporated to afford the title compound.

EXAMPLE 244-Trimethylsilyloxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

The title compound is prepared by the reaction of the compound preparedin Example 16A with chlorotrimethylsilane.

EXAMPLE 254-Benzoyloxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

A solution of 50% aqueous hydrogen peroxide is added slowly to a mixtureof 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and ferrouschloride tetrahydrate in tert-butyl alcohol at 30-60° C. Excess peroxideis decomposed by aqueous sodium sulfite solution. The organic layer isconcentrated and the residue is purified by flash chromatography toafford the title compound.

EXAMPLE 261-(2-Hydroxy-2-methylpropoxy)-4-[3-(trimethylsilyl)propoxy]-2,2,6,6-tetramethylpiperidine

The title compound is prepared by reacting the compound prepared inExample 17 with trimethylsilane and hydrogen hexachloroplatinate(IV) inisopropyl alcohol.

EXAMPLE 27Tetrakis{3-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yloxy]propyl}-1,3,5,7-tetramethylcyclotetrasiloxane

The title compound is prepared by the reaction of the compound preparedin Example 17 with 1,3,5,7-tetramethylcyclotetrasiloxane, hydrogenhexachloroplatinate(IV) in isopropyl alcohol.

EXAMPLE 28Poly{[3-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yloxy]propyl]methyl}silane

The title compound is prepared by the reaction of the compound preparedin Example 17 with poly(methylsilane) and hydrogenhexachloroplatinate(IV) in isopropyl alcohol.

EXAMPLE 29Poly{[3-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin4-yloxy]propyl]methyl}siloxane

The title compound is prepared by the reaction of the compound preparedin Example 17 with poly(methylsiloxane) and hydrogenhexachloroplatinate(IV) in isopropyl alcohol.

EXAMPLE 30 Mixture ofBis[1-(2-Hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]Glutarate andBis[1-(2-Hydroxy-2-methylpropoxy)-2,2,6,6tetramethylpiperidin4-yl]Adipate

A mixture of the compound prepared in Example 16A, DBE-2 dimethyl estermixture (DuPont), and lithium amide is heated at reflux in xylene.Methanol is distilled from the reaction mixture. The reaction mixture isquenched with dilute mineral acid, and the organic layer is washed withwater and dried over anhydrous magnesium sulfate. The xylene solution isevaporated at reduced pressure to afford the title compound mixture.

EXAMPLE 30A Mixture ofBis[1-(2-Hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]Glutarate andBis[1-(2-Hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]Succinate

When the procedure of Example 30 is repeated with DBE-9 a dimethyl estermixture (DuPont), the title mixture is prepared.

EXAMPLE 31 Reaction of Bis(1-oxyl-2,2,6,6-tetramethylpiperidin4-yl)Sebacate with Neopentyl alcohol

Aqueous hydrogen peroxide is added to a mixture ofbis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate and ferrouschloride in neopentyl alcohol according to the procedure of Example 25.

EXAMPLE 32 Reaction of 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one withNeopentyl Glycol

Aqueous hydrogen peroxide is added to a mixture of1-oxyl-2,2,6,6-tetramethylpiperidin-4-one and ferrous chloride inneopentyl glycol according to the procedure of Example 25.

EXAMPLE 33 Reaction of 4-Octadecanoyloxy-1-oxyl-2,2,6,6-piperidine withtert-Amyl Alcohol

Aqueous hydrogen peroxide is added to a mixture of4-octadecanoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and ferrouschloride in tert-amyl alcohol according to the procedure of Example 25.

EXAMPLE 344-Benzoyloxy-1-(2-hydroxycyclohexyloxy)-2,2,6,6-tetramethylpiperidine

Tributyltin hydride is added dropwise to a solution of2-bromocyclohexanol and excess4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine in chlorobenzene. Themixture is heated to facilitate reaction. The crude reaction mixture ispassed through silica gel with heptane and then heptanelethyl acetate toafford the title compound as a mixture os cis/trans isomers.

EXAMPLE 354-Hydroxy-1-(2-hydroxycyclohexyloxy)-2,2,6,6-tetramethylpiperidine

The title compound is prepared by heating the compound prepared inExample 34 in a solution of potassium hydroxide in methanol.

EXAMPLE 36 Reaction of 4-Benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidinewith Propylene Glycol

Aqueous hydrogen peroxide is added to a mixture of4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and ferrous chloridetetrahydrate in propylene glycol according to the procedure of Example25.

EXAMPLE 37 Reaction of 4-Benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidinewith Trimethylene Glycol

Aqueous hydrogen peroxide is added to a mixture of4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and ferrous chloridetetrahydrate in trimethylene glycol according to the procedure ofExample 25.

EXAMPLE 38 Bis[1-(2-hydroxyethoxy)-2,2,6,6-tetramethylpiperidin-4-yl]Sebacate

Tributyltin hydride is added dropwise to a solution of 2-iodoethanol andexcess bis(1-oxyl-_(—)2,2,6,6-tetramethylpiperidin4-yl) sebacate inchlorobenzene. The crude reaction mixture is passed through silica gelwith heptane and then heptane/ethyl acetate to afford the titlecompound.

EXAMPLE 39 Reaction of Bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)Sebacate with Isopropanol

Aqueous hydrogen peroxide is added to a mixture ofbis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate and ferrouschloride tetrahydrate in isopropanol according to the procedure ofExample 25.

EXAMPLE 40 Reaction of 4-Benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidinewith 1,4-Butanediol

Aqueous hydrogen peroxide is added to a mixture of4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and ferrous chloridetetrahydrate in 1,4-butanediol according to the procedure of Example 25.

EXAMPLE 41

Reaction of 4-Hexyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine with Pinacol

Aqueous hydrogen peroxide is added to a mixture of4-hexyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and ferrous chloridetetrahydrate in pinacol according to the procedure of Example 25.

EXAMPLE 42 Reaction of 1-Oxyl-2,2,6,6-tetramethylpiperidin-4-one withGlycerol

Aqueous hydrogen peroxide is added to a mixture of1-oxyl-2,2,6,6-tetramethylpiperidin-4-one and ferrous chloridetetrahydrate in glycerol according to the procedure of Example 25.

EXAMPLE 43 Reaction of 4-Hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidinewith 2-Ethyl-1-hexanol

Aqueous hydrogen peroxide is added to a mixture of4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine and ferrous chloridetetrahydrate in 2-ethyl-1-hexanol according to the procedure of Example25.

EXAMPLE 441-(2-Hydroxy-2-methylpropoxy)-4-hexadecanoyloxy-2,2,6,6-tetramethylpiperidine

A mixture of the compound prepared in Example 16A, methyl hexadecanoateand lithium amide is heated at reflux in xylene, Methanol is distilledfrom the reaction mixture. The reaction mixture is quenched with dilutemineral acid, and the organic layer is washed with water and dried overanhydrous magnesium sulfate. The xylene solution is evaporated atreduced pressure to afford the title compound.

EXAMPLE 44A1-(4-Hexadecanoyloxy-2,2,6,6-tetramethylpiperidin-1-yloxy)-2-hexadecanoyloxy-2-methylpropane

The title compound is prepared by the reaction of the compound preparedin Example 16A with excess methyl hexadecanoate and a catalytic amountof lithium amide in xylene.

EXAMPLE 45 Reaction ofN,N′,N″,N′″-Tetrakis{2,4-bis[N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl]butylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylaminewith Cyclohexanol

A mixture ofN,N′,N″,N′″-tetrakis{2,4-bis[N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl]butylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylaminein cyclohexanol is reacted with aqueous hydrogen peroxide and ferrouschloride tetrahydrate according to the method of Example 4. A whitesolid melting at 133-175° C. is obtained.

EXAMPLE 46 Reaction of2,4,6-Tris[N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl]butylamino}-s-triazinewith Cyclohexanol

A mixture of2,4,6-tris[N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl]butylamino}-s-triazineand cyclohexanol is reacted with aqueous hydrogen peroxide and ferrouschloride tetrahydrate according to the procedure of Example 4. A lightbrown oil is obtained.

EXAMPLE 47 Bis[1-(3-hydroxypropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]Sebacate

Tributyltin hydride is added dropwise to a solution of3-bromo-1-propanol and excessbis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate in chlorobenzene.The mixture is heated to facilitate reaction. The crude reaction mixtureis passed through silica gel with heptane and then heptane/ethyl acetateto afford the title compound.

EXAMPLE 48 Bis[1-(12-hydroxy-1-dodecyloxy)-2,2,6,6-tetramethylpiperidin-4-yl] Sebacate

Tributyltin hydride is added dropwise to a solution of12-bromo-1-dodecanol and excessbis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate in chlorobenzene.The mixture is heated to facilitate reaction. The crude reaction mixtureis passed through silica gel with heptane and then heptane/ethyl acetateto afford the title compound.

EXAMPLE 49 Bis(1-(2-hydroxypropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]Sebacate

Tributyltin hydride is added dropwise to a solution of1-bromo-2-propanol and excessbis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate in chlorobenzene.The mixture is heated to facilitate reaction. The crude reaction mixtureis passed through silica gel with heptane and then heptane/ethyl acetateto afford the title compound.

EXAMPLE 50 Reaction of the Product of Example 11 withN,N′-Bis(3-aminopropyl)ethylenediamine

N,N′-Bis(3-aminopropyl)ethylenediamine and the product prepared inExample 11 are reacted in a 1:3.0 to 1:3.5 molar ratio. The productmixture includesN,N′,N′″-tris{2,4-bis[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamine,N,N′,N′″-tris{2,4-bis[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamine,andN,N′,N″,N′″-tetrakis{2,4-bis[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino]-s-triazin-yl}-3,3′-ethylenediiminodipropylamine.

EXAMPLE 51N,N′,N″,N′″-Tetrakis{2,4-bis[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin4-yl]butylamino]-s-triazin-6-yl}3,3′-ethylenediiminodipropylamine

The title compound is prepared by the addition of aqueous hydrogenperoxide to a mixture ofN,N′,N″,N′″-tetrakis{2,4-bis[N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl]butylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamine,ferrous chloride and tert-butyl alcohol according to the procedure ofExample 7.

EXAMPLE 52 Reaction of the Product of Example 11 withN,N′-Bis(3-aminopropyl)ethylenediamine

N,N′-Bis(3-aminopropyl)ethylenediamine and the product prepared inExample 11 are reacted in a 1:4.0 molar ratio. The product mixtureincludesN,N′,N′″-tris{2,4-bis[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamine,N,N′,N′″-tris{2,4-bis[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino]-s-trazin-6-yl}3,3′-ethylenediiminodipropylamine,andN,N′,N″,N′″-tetrakis{2,4-bis[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin4-yl]butylamino]-s-triazin-6-yl}3,3′-ethylenediiminodipropylamine.

EXAMPLE 53A2{N-[1-(2-Hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino}-4,6-dichloro-s-triazine

The compound prepared in Example 23B is reacted with an equimolar amountof cyanuric chloride and sodium bicarbonate at 0° C. to give the titlecompound.

EXAMPLE 53BN,N′-Bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-1,6-hexanediamine

The title compound is prepared by the hydrogenation at 50 psi of thecompound obtained in Example 23A, hexamethylenediamine, methanol and acatalytic amount of 5% platinum on carbon.

EXAMPLE 53CN,N′-Bis{2-[N-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino]-4-chloro-s-triazin-6-yl)-N,N′-bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-1,6-hexanediamine

The title compound is prepared by reaction of the two compounds preparedin Examples 53A and 53B in a 2:1 molar ratio in xylene at 60-80° C. withsodium hydroxide as the acid acceptor.

EXAMPLE 53D Oligomer ofN-{2-[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino]-s-triazin-4-yl)

N,N′-bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-1,6-hexanediamine terminated with 2,4-bis(dibutylamino)-s-triazin-6-yl

The compounds prepared in Examples 53B and 53C are mixed together in a2:1 molar ratio in xylene solution at 100-160° C. with sodium hydroxideas the acid acceptor. The reaction mixture is then treated with2,4-bis(dibutylamino)-6-chloro-s-triazine under the same conditions togive an oligomeric product having a low number (2, 4, 6, 8) of repeatingunits terminated by the 2,4-bis(dibutylamino)-s-triazin-6-yl moieties asseen in the structure below.

EXAMPLE 54 Oligomer ofN-{2-[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino]-s-triazin-4-yl}-N,N′-bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-1,6-hexanediamine terminated with 2,4-bis(dibutylamino)-s-triazin-6-yl

N,N′-Bis(2,2,6,6-tetramethylpiperidin-4-yl)-1,6-hexanediamine andN,N′-bis{2-[N-(2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-4-chloro-s-trazin-6-yl}N,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)-1,6-hexanediamineare mixed together in a 2:1 molar ratio in xylene at 100-160° C. withsodium hydroxide as the acid acceptor. The reaction mixture is thentreated with 2,4-bis(dibutylamino)-6-chloro-s-triazine under the sameconditions. The resulting mixture of oligomers is heated with tert-butylhydroperoxide and a catalytic amount of molybdenum trioxide in an inertsolvent such as 1,2-dichloroethane to form the corresponding N-oxylcompounds. Aqueous hydrogen peroxide in then added to the mixture of theN-oxyl compounds and ferrous chloride tetrahydrate in tert-butyl alcoholaccording to the procedure of Example 7. The final products is a mixtureof oligomers as in Example 53D although the ratios of the individualcomponents may not be the same as in Example 53D.

EXAMPLE 55 Oligomer ofN-{2-[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino]-s-triazin-4-yl}-N,N′-bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-1,6-hexanediamineterminated with2-butylamino4{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-butylamino-s-triazin-6-yl

The title compound is prepared by heating a mixture of the compoundsprepared in Examples 53A and 53B, in a 1.33 to 1.0 molar ratio in xyleneat 100-160° C. using sodium hydroxide as the acid acceptor. Dibutylamineis then added to the reaction mixture under the same conditions tocomplete the reaction. The product is a mixture of oligomers thatinclude 1-4 repeating units as seen in the structure below.

EXAMPLE 56 Oligomer ofN-{2-[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino]-s-triazin-4-yl}-N,N′-bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-1,6-hexanediamineterminated with2-butylamino-4-{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin4-yl]-butylamino-s-triazin-6-yl

The title compound is prepared by heating a mixture of the compoundsprepared in Examples 53B and 53C, in a 0.5:1 molar ratio in xylene at100-160° C. using sodium hydroxide as the acid acceptor. Dibutylamine isthen added to the reaction mixture under the same conditions to completethe reaction. The product is a mixture of oligomers that include 1, 3, 5and 7 repeating units as seen in the structure below.

EXAMPLE 57 Oligomer ofN-{2-[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino]-s-triazin4-yl}-N,N′-bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-1,6-hexanediamineterminated with2-butylamino-4-{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-butylamino-s-triazin-6-yl

N,N′-Bis(2,2,6,6-tetramethylpiperidin-4-yl)-1,6-hexanediamine andN,N′-bis{2-[N-(2,2,6,6-tetramethylpiperidin-4-yl)butylamino]4-chloro-s-triazin-6-yl}N,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)-1,6-hexanediamineare mixed together in a 0.5:1 molar ratio in xylene at 100-160° C. withsodium hydroxide as the acid acceptor. The reaction mixture is thentreated with dibutylamine under the same conditions. The resultingmixture of oligomers is treated with tert-butyl hydroperoxide and acatalytic amount of molybdenum trioxide in an inert solvent such as1,2-dichloroethane to form the corresponding N-oxyl compounds. Aqueoushydrogen peroxide in then added to a mixture of the N-oxyl compounds andferrous chloride tetrahydrate in tert-butyl alcohol according to theprocedure of Example 7. The final product is a mixture of oligomers suchas prepared in Example 56 although the ratios of the individualcomponents may not be the same as those in the product of Example 56.

EXAMPLE 58 Oligomer ofN-{2-[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino]-s-triazin-4-yl}-N,N′-bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-1,6-hexanediamineterminated with Acetyl

The compounds prepared in Examples 53B and 53C are mixed together in a2:1 molar ratio in xylene at 100-160° C. using sodium hydroxide as theacid acceptor. After the reaction is complete, the reaction mixture isconcentrated at reduced pressure. Acetic anhydride is added to thereaction mixture at room temperature, and the mixture is then heated at130° C. The crude mixture is cooled and neutralized with potassiumcarbonate. The reaction mixture is concentrated at reduced pressure. Theproduct is a mixture of oligomers that include 2, 4, and 6 repeatingunits as seen in the structure below.

EXAMPLE 59 Oligomer ofN-{2-[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino]-s-triazin-4-yl}-N,N′-bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-1,6-hexanediamineterminated with Acetyl

Example 54 is repeated except that acetic anhydride is used in place of2,4-bis(dibutylamino)-6-chloro-s-triazine according to the procedure ofExample 58. The final product is a mixture of oligomers as described inExample 58 although the ratios of the components may not be identical tothose of the product prepared in Example 58.

EXAMPLE 60Poly[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-ylMethacrylate

The title compound is prepared from the free radical polymerization ofthe compound obtained in Example 16B. The average molecular weight ofthe polymer is 1500-3000 amu.

EXAMPLE 61Poly[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-ylAcrylate

The title compound is prepared from the free radical polymerization ofthe compound obtained in Example 21. The average molecular weight of thepolymer is 1500-3000 amu.

EXAMPLE 62 1,4-Bis(4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yloxy)-2-butanol

Tributyltin hydride is added dropwise to a solution of1,4-dibromo-2-propanol and excess4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine in chlorobenzene. Themixture is heated to facilitate the reaction. The crude reaction mixtureis passed through silica gel with heptane and then heptane/ethyl acetateto afford the title compound.

EXAMPLE 63 1,3-Bis(4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yloxy)-2-propanol

Tributyltin hydride is added dropwise to a solution of1,3-dibromo-2-propanol and excess4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine in chlorobenzene. Themixture is heated to facilitate the reaction. The crude reaction mixtureis passed through silica gel with heptane and then heptanelethyl acetateto afford the title compound.

EXAMPLE 64 2-Hydroxy-2-methylpropane-1,3-diylbis{[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl](1-oxy-2,2,6,6-tetramethylpiperidin4-yl) Sebacate

The title compound is isolated by high pressure liquid chromatographyfrom the crude reaction product obtained in Example 2.

EXAMPLE 65 1,3-Bis(4-octadecanoyloxy-2,2,6,6-tetramethylpiperidin-1-yloxy)-2-methyl-2-propanol

Aqueous hydrogen peroxide is added to a mixture of4-octadecanoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and ferrouschloride tetrahydrate in tert-butyl alcohol at 30-50° C. Excess peroxideis decomposed with aqueous sodium sulfite solution. The organic layer isconcentrated to obtain a mixture which includes1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidineand the title compound. The title compound is separated from the mixtureby high pressure liquid chromatography.

EXAMPLE 66 1,3-Bis(4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yloxy)-2-methyl-2-propanol

The title compound is isolated by high pressure liquid chromatographyfrom the crude reaction product obtained in Example 16A.

EXAMPLE 67 1,3-Bis(4-oxo-2,2,6,6-tetramethylpiperidin-1-yloxy)-2-methyl-2-propanol

The title compound is isolated by high pressure liquid chromatographyfrom the crude reaction product obtained in Example 23A.

EXAMPLE 681-(2-Hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-ylHexanoate

The title compound is prepared by heating a mixture of methyl hexanoate,the compound prepared in Example 16A, lithium amide and xylene at refluxwhile methanol is removed by distillation.

EXAMPLE 694-Benzoyloxy-1-(2-hydroxyethoxy)-2,2,6,6-tetramethylpiperidine

Tributyltin hydride is added dropwise to a solution of 2-iodoethanol and4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine in chlorobenzene. Thecrude reaction mixture is passed through silica gel with heptane andthen heptanelethyl acetate to afford the title compound.

EXAMPLE 70 4-Hydroxy-1-(2-hydroxyethoxy)-2,2,6,6-tetramethylpiperidine

The title compound is prepared by heating a methanolic solution of thecompound obtained in Example 69 with potassium hydroxide.

EXAMPLE 71Poly[4-hydroxy-1-(2-hydroxyethoxy)-2,2,6,6-tetramethylpiperidin-4-ylsuccinate]

The title compound is prepared by the reaction of approximatelyequimolar amounts of dimethyl succinate and the compound prepared inExample 70.

EXAMPLE 72Poly[4-hydroxy-1-(2-hydroxycyclohexyloxy)-2,2,6,6-tetramethylpiperidin-4-ylsuccinate]

The title compound is prepared by the reaction of approximatelyequimolar amounts of dimethyl succinate and the compound prepared inExample 35.

EXAMPLE 731-(2-Hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine

A mixture of methyl stearate, the compound prepared in Example 16A and acatalytic amount of lithium amide is heated at reflux in xylene.Methanol is distilled from the reaction mixture. The reaction isquenched with dilute acid. The organic layer is concentrated and thecrude product is purified by flash chromatography on silica gel toafford the title compound as a white solid melting at 51-56° C.

EXAMPLE 73A 1-(4-Octadecanoyloxy-2,2,6,6-tetramethylpiperidin-1-yloxy)-2-octadecanoyloxy-2-methylpropane

The title compound is prepared by the reaction of the compound preparedin Example 16A with excess methyl stearate and a catalytic amount oflithium amide in xylene.

EXAMPLE 744-Hydroxy-1-(2-hydroxy-1-phenethoxy)-2,2,6,6-tetramethylpiperidine

The title compound is prepared by heating a methanolic solution of thecompound obtained in Example 10 with potassium hydroxide.

EXAMPLE 75Poly[4-hydroxy-1-(2-hydroxy-1-phenylethoxy)-2,2,6,6-tetramethylpiperidin-4-ylsuccinate]

The title compound is prepared by the reaction of approximatelyequimolar amounts of dimethyl succinate and the compound obtained inExample 74.

EXAMPLE 76 Stabilization of Thermoplastic Olefins

Molded test specimens are prepared by injection molding thermoplasticolefin (TPO) pellets containing pigments, a phosphite, a phenolicantioxidant or hydroxylamine, a metal stearate, ultraviolet lightabsorbers or a hindered amine stabilizer or a mixture of UV absorber andhindered amine stabilizer.

Pigmented TPO pellets are prepared from pure pigment or pigmentconcentrate, coadditives and commercially available TPO by mixing thecomponents in a Superior/MPM 1″ single screw extruder with a generalall-purpose screw (24:1 UD) at 400° F. (200° C.), cooled in a water bathand pelletized. The resulting pellets are molded into 60 mil (0.006inch), 2Δ×2″ plaques at about 375° F. (190° C.) on a BOY 30M InjectionMolding Machine.

Pigmented TPO formulation composed of polypropylene blended with arubber modifier where the rubber modifier is an in-situ reactedcopolymer or blended product containing copolymers of propylene andethylene with or without a ternary component such as ethylidenenorbornene are stabilized with a base stabilization system consisting ofan N,N-dialkylhydroxylamine or a hindered phenolic antioxidant with orwithout an organophosphorus compound.

All additive and pigment concentrations in the final formulation areexpressed as weight percent based on the resin.

Formulation contained thermoplastic olefin pellets and one or more ofthe following components:

0.0 to 2.0% pigment,

0.0 to 50.0% talc,

0.0 to 0.1% phosphite,

0.0 to 1.25% phenolic antioxidant,

0.0 to 0.1% hydroxylamine

0.05 to 0.10 calcium stearate,

0.0 to 1.25% UV absorber

0.0 to 1.25% hindered amine stabilizer.

The components are dry-blended in a tumble dryer prior to extrusion andmolding.

Test plaques are mounted in metal frames and exposed in an Atlas Ci65Xenon Arc Weather-Ometer at 70° C. black panel temperature, 0.55 W/m² at340 nonometers and 50% relative humidity with intermittent light/darkcycles and water spray (Society of Automotive Engineers—SAE J 1960 TestProcedure). Specimens are tested at approximately 625 kilojouleintervals by performing color measurements on an Applied Color Systemsspectrophotometer by reflectance mode according to ASTM D 2244-79. Datacollected include delta E, L*, a* and b* values. Gloss measurements areconducted on a BYK-Gardner Haze/Gloss Meter at 60° according to ASTM D523.

UV Exposure Testing

Test speciments exposed to UV radiation exhibit exceptional resistanceto photodegration when stabilized with light stabilizer systemscomprising a combination of2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole (TINUVIN®328,Ciba), the compound of Example 73 andN,N′,N″,N′″-tetrakis[4,6-bis(butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino)-s-triazin-2-yl]-1,10-diamino-4,7-diazadecane(CHIMASSORB® 119, Ciba). The control sample consists of a stabilizerformulation commonly used in the industry to impart UV stability. All ofthe samples contain a pigment, Pigment Red 177, and talc.

The test plaques described earlier contain the following (allconcentrations are weight percent based on resin):

Polymer substrate is commercially available polyolefin blend POLYTROPE®TPP 518-01 supplied by A. Schulman Inc. Akron, Ohio)

Color package is 0.025% Red 3B -Pigment Red 177, C.I. #65300.

Each plaque contains:

0.2% TINUVIN® 328;

0.1% calcium stearate; and

15% talc.

The Control plaques additionally contain

0.1% IRGANOX® B225 (50:50 blend of IRGANOX® 1010, Ciba(neopentanetetrayl tetrakis(4-hydroxy-3,5-di-tert-butylhydrocinnamate)and IRGAFOS® 168, Ciba [tris-(2,4-di-tert-butylphenyl) phosphite;

0.2% TINUVIN® 770, Ciba [bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate];

0.2% CHIMASSORB 944, Ciba [polycondensation product of4,4′-hexamethylene-bis(amino-2,2,6,6-tetramethylpiperidine) and2,4-dichloro-6-tert-octylamino-s-triazine].

The two test plaques (NOR-1 and NOR-2) each contain 0.05%N,N,-dialkylhydroxylamine;

NOR-1 additionally contains

0.2% of CHIMASSORB® 119; and

0.2% of TINUVIN® 123, Ciba,[bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate].

NOR-2 additionally contains

0.2% of CHIMASSORB® 119; and

0.2% of the compound of Example 73.

The results of the UV testing are given in the table below.

DE* Gloss Value % Gloss Value 0 3000 0 3000 0 3000 Sample Kj/m² Kj/m²Kj/m² Kj/m² Kj/m² Kj/m² control 0.0 4.7 66.6 5.4 100 8.1 NOR-1 0.0 4.065.5 16.9 100 25.8 NOR-2 0.0 3.8 64.9 45.3 100 69.8

The compound of Example 73 present in test plaques NOR-2 specificallyshows greatly improved gloss retention compared to the less effectivecontrol system and in fact is also more effective that a relatedhindered amine compound (TINUVIN® 123) present in test plaques NOR-1.Resistance to color change upon UV exposure is also enhanced.

Polymer blends containing an unsaturated ternary component, such as EPDMblends, are especially benefited with the more efficient instant lightstabilizer systems described above.

In all cases, the light stabilized formulations show much greatedresistance to photodegradation than unstabilized specimens which failquickly under the UV exposure conditions outlined above.

EXAMPLE 77 Paintable TPO

Molded test specimens are prepared by injection molding thermoplasticolefin (TPO) pellets containing the instant compounds, pigments andother coadditives as described in Example 76.

The light stable formulations are painted with one-pack paint systemsand tested for TPO/paint interactions. Before painting, the testspecimens are first washed in accordance with GM998-4801 and dried for15 minutes at 200° F. (94° C.). Adhesion promoter is applied to the dryfilm thickness of 0.2-0.4 mils. The samples are dried for five minutesbefore a 1K basecoat is applied to a film thickness of 1.2-1.4 mils. Thepainted panels are dried for three minutes, a clearcoat is then appliedto a dry film thickness of 1.2-1.5 mils followed by ten minutes flashdrying and a 30 minute oven bake at 250° F. (121° C.).

Paint adhesion is measured by Aggressive Adhesion Testing (proprietarytest procedure conducted at Technical Finishing, Inc.) and Taber Scuff.Painted panels which retain greater than 80% of the paint finish areconsidered acceptable. After Aggressive Adhesion Testing, samples withless than 5% paint loss are deemed acceptable.

Samples are tested to evaluate the TPO/paint interactions as follows:

Aggresive HALS Formulation* Taber Scuff Test Adhesion Test pK_(a) A 100%removed 6% Loss (fail) 9.1 B  0% removed 4% Loss (pass) 4.6 C  0%removed 3% Loss (pass) 4.0

Formulation A contains 0.2% CHIMASSORB® 944, 0.2% TINUVIN® 328, 500 ppmcalcium stearate and 750 ppm N,N-dialkylhydroxylamine in reactor-gradeTPO.

A also contains 0.2% of bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate(TINUVIN® 770, pK_(a) of 9.1).

Formulations B and C contain 0.2% CHIMASSORB® 119, 0.2% TINUVIN® 328,500 ppm calcium stearate and 750 ppm N,N-dialkylhydroxylamine inreactor-grade TPO. 1

B also contains 0.2% ofbis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate (TINUVIN®123, pK_(a) of 4.6).

C also contains 0.2% of1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine(compound of Example 73, pK_(a) of 4.0)

The data in the table indicate that, although formulation A failed inboth the Taber Scuff and Aggressive Adhesion Tests, both formulations Band C passed both paint adhesion tests. However, as inspection of thepK_(a) values attests, the lower the pK_(a) value (less basic) for thetest hindered amine compound the less paint loss results in thisAggressive Adhesion Test. The instant compound of Example 73 having thehydroxyl moiety present has the lowest pK_(a) value and also the leastpaint loss even better than the close prior art compound where nohydroxyl moiety is present.

EXAMPLE 78 Stabilization of Polypropylene Molded Articles

Molded test specimens are prepared by injection molding polypropylenepellets containing pigments, a phosphite, a phenolic antioxidant orhydroxylamine, a metal stearate, ultraviolet light absorbers or ahindered amine stabilizers or a mixture of UV absorbers and hinderedamine stabilizers.

Pigmented polypropylene pellets are prepared from pure pigment orpigment concentrates, stabilizers, co-additives and commerciallyavailable polypropylene by mixing the components in a Superior/MPM 1″single screw extruder with a general all-purpose screw (24:1 L/D) at475° F. (250° C.), cooled in a water bath and pelletized. The resultingpellets are molded into 60 mil (0.06 inch thick) 2″×2″ plaques at about475° F. (250° C.) on a BOY 30M Injection Molding Machine.

Pigmented polypropylene formulations composed of polypropylenehomopolymer or polypropylene copolymer are stabilized with a basestabilization system consisting of an N,N-dialkylhydroxylamine or ahindered phenolic antioxidant with or without an organophosphorouscompound.

All additive and pigment concentrations in the final formulations areexpressed as weight percent based on the resin.

Formulations contained polypropylene pellets and one or more of thefollowing components;

0.0%-2.0% pigment,

0.0%-50.0% talc,

0.0%-50.0% calcium carbonate,

0.0%-0.1% phosphite,

0.0%-1.25% phenolic antioxidant,

0.0%-0.1% hydroxylamine,

0.05%-0.10% calcium stearate,

0.0%-1.25% UV absorber,

0.0%-1.25% hindered amine stabilizer.

The components are dry blended in a tumble dryer prior to extrusion andmolding.

Test plaques are mounted in metal frames and exposed in an Atlas Ci65Xenon Arc Weather-o-meter at 70° C. black panel temperature, 0.55 W/m²at 340 nanometers and 50% relative humidity with intermittent light/darkcycles and water spray (Society of Automotive Engineers—SAE J 1960 TestProcedure). Specimens are tested at approximately 625 kilojouleintervals by performing color measurements on an Applied Color Systemsspectrophotometer by reflectance mode according to ASTM D 2244-79. Datacollected included delta E, L*, a* and b* values. Gloss measurements areconducted on a BYK-GARDNER Haze/Gloss Meter at 60° according to ASTMD523.

UV Exposure Testing

Test specimens exposed to UV radiation exhibit exceptional resistance tophotodegradation when stabilized with light stabilizer systems comprisedof a combination of Tinuvin 328, the compound of Example 73 and CGL2020. CGL 2020 is oligomer ofN-{[2-(N-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazin-4-yl}N,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)-1,6-hexanediamineterminated with 2,4bis(dibutylamino)-s-triazin-6-yl. The Control sampleconsists of a stabilizer formulation commonly used in the industry toimpart UV stability. All of the samples contain Pigment Red 177.

Red 3B Formulations DE* Gloss Values % Gloss Retention Comp. 1 Comp. 2Comp. 3 0 Kj/m² 3000 Kj/m² 0 Kj/m² 3000 Kj/m² 0 Kj/m² 3000 Kj/m² Control0.14% 0.20% 0.2% Tin. 0 6.5 88% 24% 100% 28% T 123 CGL 2020 328 Ex. 730.10% 0.10% 0.1% Tin. 0 0.6 88% 77% 100% 88% Ex. 73 CGL 2020 328 NOR 20.10% 0.10% 0.1% Tin. 0 8.2 87% 13% 100% 14% NOR 2 CGL 2020 328

All formulations are base stabilized with 0.05% dialklyhydroxylamine inthe final resin formulation.

Polymer substrate is a commercially available polypropylenehomopolymer—Profax 6501 (commercial supplier Montell Polyolefins).

Color package is 0.25% Red 3B—Pigment Red 177, C.I. # 65300 in the finalresin formulation.

Each formulation contains a hydroxyphenyl benzotriazole UVabsorber—Tinuvin 328,2-(2-hydroxy-3,5di-tert-amylphenyl)-2H-benzotriazole.

NOR 2 isbis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)succinate.

Each formulation contains 0.1% calcium stearate.

Samples are 60 mil thick 2″×2″ injection molded plaques.

UV exposures conducted under SAE J 1960—Exterior Automotive conditions.

All additive and pigment concentrations in the final formulations areexpressed as weight percent on the resin.

The formulation containing the subject compound of Example 73specifically shows greatly improved gloss retention compared to the lesseffective Control stabilizer system even at a lower total concentration.Resistance to color change upon UV exposure is also significantlyenhanced. The subject compound of Example 73 is also significantly moreeffective in maintaining appearance when compared with another solidN—O—R HALS (NOR 2) of similar molecular at equal concentrations.

In all cases, the light stabilized formulations show much greaterresistance to photodegradation than unstabilized specimens which failquickly under the UV exposure conditions outlined above.

EXAMPLE 79 Polypropylene Fiber

Fiber samples are prepared by extruding fiber-grade polypropylene withthe instant compounds, coadditives and pigments. Typical formulationscontain the instant compounds at levels from 0.05 to 2.0%, a metalstearate such as calcium stearate at 0.05 to 0.5%, pigments from 0 to5%, UV absorbers at levels of 0.05 to 2.0%, phosphites at 0 to 0.1%,phenolic antioxidants at 0 to 1.25%, N,N-dialkylhydroxylamines at 0 to0.1% and optionally other hindered amines at levels of 0 to 2.0%. Alladditive and pigment concentrations in the final formulations are givenas weight percent based on the resin.

Pigment concentrates are prepared from pure pigment and polypropylene(PROFAX®, Hercules) by mixing the two components in a high shear mixerin a ratio of 25% pigment and 75% resin, pressing the resultingresin/pigment mixture on a Wabash Compression molder (Model #30-1515-4T3) into a thin sheet and dividing the sheet into fine chipsfor dispersion in polypropylene at reduced concentrations.Alternatively, pigment concentrates are obtained as pigment dispersionsin a suitable carrier resin for subsequent blending in fiber at reducedconcentrations.

Formulations containing polypropylene, 0.05-0.1% phosphite, 0-1.25%phenolic antioxidant, 0-0.1% dialkylhydroxylamine, 0.05-0.1% calciumstearate, 0-1.25% UV absorber, 0-1.25% hindered amine are dry blended ina tumble dryer, extruded on a Superior/MPM 1″ single screw extruder witha general all-purpose screw (24:1 UD) at 475® F. (246° C.), cooled in awater bath and pelletized. The resulting pellets are spun into fiber atabout 475® F. (246° C.) on a HILLS Research Fiber Extruder (Model #REM-3P-24) fitted with a 41 hole, delta configuration spinneret. Thespun tow is stretched at a draw ratio of 3.2:1 producing a final denierof 615/41.

Fiber samples are knitted into socks on a Lawson-HemphillFiber AnalysisKnitter, cut into appropriate lengths and exposed in an Atlas Ci65 XenonArc Weather-O-meter at 89° C. black panel temperature, 0.55 W/m² at 340nanometers and 50% relative humidity (Society of AutomotiveEngineers—SAE J 1885 Test Procedure).

Fiber samples are tested by performing color measurements on an AppliedColor Systems spectrophotometer by reflectance mode according to ASTM D2244-79. Identical, but separate, fiber samples are examined forcatastrophic failure and the time to failure is recorded.

The samples containing the instant compounds exhibit good stabilizationperformance against the deleterious effects of UV light.

EXAMPLE 80

Other socks of propylene fiber as prepared in Example 79 are exposed ina Blue M forced draft oven at 120° C. Failure is determined by thecriterion set forth in Example 79. The longer it takes for thecatastrophic failure to occur, the more effective is the stabilizingsystem.

The socks containing the instant compounds exhibit good thermalstabilization efficacy.

EXAMPLE 81

Film grade polyethylene is dry blended with approximately 10% by weightof the test additives, such as the compound of Example 51, and then meltcompounded at 200° C. into “Masterbatch” pellets. The fully formulated“Masterbatch” pellets are dry blended with polyethylene resin to get thedesired final stabilizer concentrations. Typical formulations containthe instant compounds at levels from 0.05% to 2.0%, a metal stearatesuch as calcium stearate at 0.05% to 0.5%, a phosphite at 0% to 0.1%, aphenolic antioxidant at 0% to 1.25%, an N,N-dialkylhydroxylamine at 0%to 0.1% and optionally a hindered amine at 0% to 2.0%. The Thisstabilized fully formulated resin is then blown at 200° C. into a 150micron thick film on a DOLCI film line.

The blown films are exposed in an Atlas Xenon-Arc WeatherOmeteraccording to ASTM G26 at 63° C. bpt, 0.35 W/m² at 340 nm with no spraycycle. Films are tested periodically for any change in elongation usingan Instron 112 tensile tester. Failure in this test is determined byobservation of the loss of % elongation in the film. The longer it takesfor this loss to occur, th more effective is the stabilizer system.

The films containing the instant compound mixture show good lightstabilizing efficacy.

EXAMPLE 82

Film grade polyethylene is dry blended with 10% loading of the testadditives, such as the compound of Example 51, as described in Example81, and then melt compounded at 200° C. into fully formulated masterbatch pellets. The master batch pellets are dry blended with thepolyethylene resin to get the final stabilizer concentration. The fullyformulated resin is then blown at 200° C. into a 150 micron thick filmusing a DOLCI film line.

The resulting films are exposed on a greenhouse on galvanized ironbacking. Treatment includes applications of pesticides on a regularbasis (i.e. sodium N-methyldithiocarbamate, VAPAM′ every six months andSESMETRIN′ every month). Performance is measured by monitoring thepercent residual elongation. Failure is defined as the time to a 50%loss of original elongation.

The films containing the instant compounds show good resistance topesticides.

EXAMPLE 83

Master batch pellets prepared as described in Example 81 are dry blendedinto polyethylene resin to get the final stabilizer concentration. Thefully formulated resin is then blown at 200° C. into a 25 micron thickfilm using a DOLCI film line.

The resulting films are exposed on a soil to simulate agricultural mulchfilm conditions. Treatment includes exposure to methyl bromide fumigantfor three days at 60 g/m³. Performance is measured by monitoring thetime to physical embrittlement.

The films containing the instant compounds show good resistance tofumigants.

EXAMPLE 84

Greenhouse film samples are prepared as described in Example 81, but inaddition to the instant compounds also contain a metal stearate or ametal oxide. Typical formulations contain from 0.05 to 2% by weight ofthe instant hindered amines, 0.05 to 0.5% of a metal stearate such ascalcium oxide, and 0.05 to 0.5% of a metal oxide such as zinc oxide ormagnesium oxide.

Effectiveness is monitored as described in Example 82. The filmscontaining the instant compounds exhibit good light stability.

EXAMPLE 85

Polypropylene fiber is prepared as described in Example 79. In additionto the instant compounds, selected halogenated flame retardants are alsoincluded in the formulation. The flame retardants aretris(3-bromo-2,2-bis(bromomethyl)propyl)phosphate, decabromodiphenyloxide, ethylene bis-(tetrabromophthalimide), or ethylenebis-(dibromo-norbomanedicarboximide).

Using the criterion for light stabilization described in Example 79, thesocks knitted from the polypropylene fiber containing the instantcompounds exhibit good light stability.

EXAMPLE 86

Molding grade polypropylene is dry blended with test additives and thenmelt compounded into pellets. In addition to the instant compounds,selected flame retardants are also included. The flame retardants aretris(3bromo-2,2-bis(bromomethyl)propyl)phosphate, decabromodiphenyloxide, ethylene bis-(tetrabromophthalimide), or ethylenebis-(dibromo-norbomanedicarboximide). The pelletized fully formulatedresin is then injection molded into test specimens using a Boy 50Mlaboratory model injection molder.

Test plaques are mounted in metal frames and exposed in an Atlas Ci65Xenon Arc Weather-Ometer with intermittent light/dark cycles and waterspray following the ASTM G26 test procedure. Specimens are tested atperiodic intervals for changes in tensile properties. Failure in thistest is determined by the observation of the loss of tensile properties.The longer it takes for the loss in properties to occur, the moreeffective is the stabilizer system.

The test samples containing the instant compounds exhibit good lightstabilization properties.

EXAMPLE 87

Molded test specimens are prepared by injection molding thermoplasticolefin (TPO) pellets as described in Example 76. In addition to theinstant compounds, selected flame retardants are also included in thetest specimens. The flame retardants aretris(3-bromo-2,2-bis(bromomethyl)propyl) phosphate, decabromodiphenyloxide, ethylene bis-(tetrabromophthalimide), or ethylenebis-(dibromo-norbomanedicarboximide).

The samples including the instant hindered amines exhibit good lightstabilizing activity.

EXAMPLE 88

Film grade polyethylene is compounded and blown into film at 200° C. asdescribed in Example 82 using a DOLCI film line. In addition to theinstant compounds, selected flame retardants are included in theformulation. The flame retardants aretris(3bromo-2,2-bis(bromomethyl)propyl) phosphate, decabromodiphenyloxide, ethylene bis-(tetrabromophthalimide), or ethylenebis-(dibromo-norbomanedicarboximide).

When tested for light stabilizing activity as described in Example 82,the films containing the instant compounds exhibit good stabilization.

EXAMPLE 89

Molded test specimens are prepared by injection molding thermoplasticolefin (TPO) pellets containing the instant compounds, pigments andother coadditives as described in Example 77.

The test specimens are painted with one-pack paint systems and testedfor TPO/paint interactions. Before painting, the test specimens arefirst wiped with isopropanol and air blasted to remove any dust. After afive minute flash, these specimens are coated with the adhesionpromoter, then the base coat, and then optionally a clear coat. Typicalfilm thickness of these various coatings are 0.1-0.3 mils for theadhesion promoter, 0.6-0.8 mils for the base coat, and 1.2-1.5 mils forthe clear coat. After painting, the specimens are cured in an over at120° C. for 30 minutes.

Samples are tested to evaluate the TPO/paint interactions as follows: Inthe initial adhesion test, a clear cellophane adhesive tape is used topull on a 3 mm cross hatched paint surface or; in the humidity test, thepainted plaques are exposed for 240 hours at 38° C. in an atmospherehaving 98% relative humidity. The blister rating is tested by visualobservation according to ASTM D 714.

The samples containing the instant compounds exhibit good TPO/paintinteraction properties as determined by the criteria above.

EXAMPLE 90 Thermoplastic Elastomers

Resin materials of the general class known as thermoplastic elastomers,examples of which include, copolymers of styrene with butadiene orisoprene and/or ethylene-cobutylene such as SBS, SEBS and SIS, are dryblended with the instant compounds and melt compounded into pellets.Typical formulations contain the instant compounds at levels from 0.05%to 2.0%, a metal stearate such as calcium stearate at 0.05% to 0.5%,pigments from 0% to 5%, UV absorbers at levels of 0.05% to 2.0%,phosphites at 0.0%-0.1%, phenolic antioxidants at 0.0%-1.25%,N,N-dialkylhydroxylamine at 0.0%-0.1%, and optionally other hinderedamine stabilizers at levels of 0.0% to 2.0%.

The pelletized fully formulated resin is then processed into a usefularticle such as blown or cast extrusion into film; injection molded intoa molded article; thermoformed into molded articles; extruded into wireand cable housing; or rotational molded into hollow articles.

The materials containing the instant compounds exhibit stability againstdeleterious effects of UV light and thermal exposure.

EXAMPLE 91

Articles prepared according to Example 90 which additionally containselected organic pigments as well as the instant compounds also exhibitstability against the deleterious effects of actinic light and thermalexposure.

EXAMPLE 92

Articles prepared according to Example 90 which additionally contain ahindered phenolic antioxidant selected from the group consisting ofneopentanetetrayl tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate,octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate,1,3,5-trimethyl-2,4,6-tris(3,5,-di-tert-butyl-4-hydroxybenzyl)benzene,1,2-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazine, calcium[bis(monoethyl 3,5-di-tert-butyl-4-hydroxybenzyl)-phosphonate],1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate and1,3,5-tris(3-hydroxy-4-tert-butyl-2,6-dimethylbenzyl) isocyanurate, aswell as the instant compounds also exhibit stability against thedeleterious effects of actinic light and thermal exposure.

EXAMPLE 93

Articles prepared according to Example 90 which additionally contain anorganophosphorus stabilizer selected from the group consisting oftris(2,4-di-tert-butylphenyl) phosphite,bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite,2,2′,2″-nitrilo[triethyl-tris-(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite], tetrakis(2,4-di-butylphenyl) 4,4′-biphenylenediphosphonite,tris(nonylphenyl) phosphite, bis(2,4-di-tert-butylphenyl)pentaerythrityl diphosphite, 2,2′-ethylidenebis(2,4-di-tert-butylphenyl)fluorophosphite and 2-butyl-2-ethylpropan-1,3-diyl2,4,6-tri-tert-butylphenyl phosphite as well as the instant compounds ofalso exhibit stability against the deleterious effects of actinic lightand thermal exposure.

EXAMPLE 94

Articles prepared according to Example 90 which additionally contain abenzofuranone stabilizer which is5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-2H-benzofuran-2-one, as well asthe instant compounds also exhibit stability against the deleteriouseffects of UV light and thermal exposure.

EXAMPLE 95

Articles prepared according to Example 90 which additionally contain adialkylhydroxylamine stabilizer which is N,N-dialkylhydroxylamine madeby the direct oxidation of N,N-di(hydrogenated tallow)amine as well asthe instant compounds also exhibit stability against the deleteriouseffects of actinic light and thermal exposure.

EXAMPLE 96

Articles prepared according to Example 90 which additionally containother hindered amine stabilizers selected from the group consisting ofbis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate, the polycondensationproduct of I-(2-hydroxyethyl)2,2,6,6-tetramethyl-4-hydroxypiperidine andsuccinic acid,N,N′,N″,N′″-tetrakis[4,6-bis(butyl-1,2,2,6,6-pentamethylpiperidin-4-yl)amino-s-triazin-2-yl]-1,10-diamino-4,7-diazadecane,the polycondensation product of4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine) and2,4-dichloro-6-tert-octylamino-s-triazine, the polycondensation productof 4,4′-hexamethylenebis(amino-2,2,6,6tetramethylpiperidine) and2,4-dichloro-6-morpholino-s-triazine, 2,2,6,6-tetramethylpiperidin-4-yloctadecanoate,3-dodecyl-1-(1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl)-pyrrolidin-2,5-dione,1,3,5-tris(N-cyclohexyl-N-[2-(2,2,6,6-tetramethylpiperazin-3-on-4-yl)ethyl]amino)-s-triazine,poly[methyl 3-(2,2,6,6-tetramethylpiperidin-4-yloxy)propyl]siloxane, thepolycondensation product of2,4-dichloro-6-(2,2,6,6-tetramethylpiperidin-4-yl)butylamino)-s-triazineand2,2′ethylene-bis{[2,4-(2,2,6,6-tetramethylpiperidin-4-yl)butylamino-s-triazin-6-yl]amino-trimethyleneamino}as well as the instant compounds also exhibit stability against thedeleterious effects of actinic light and thermal exposure.

EXAMPLE 97

Articles prepared according to Example 90 which additionally containother N-hydrocarbyloxy substituted hindered amines selected from thegroup consisting of bis(1-octyloxy-2,2,6,6-tetramethylpiperidin4-yl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate,bis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate,bis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, and1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl octadecanoate as wellas the instant compounds also exhibit stability against the deleteriouseffects of actinic light and thermal exposure.

EXAMPLE 98

Articles prepared according to Example 90 which additionally contain ao-hydroxyphenyl-2H-benzotriazole, a hydroxyphenyl benzophenone or ao-hydroxyphenyl-s-triazine UV absorber selected from the groupconsisting of 2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole,2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole,5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole,2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole,2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole,2,4-di-tert-butylphenyl 3,5-di-tert-butyl4-hydroxybenzoate,2-hydroxy-4-n-octyloxybenzophenone and2,4-bis(2,4-dimethyphenyl)-6-(2-hydroxy4-octyloxyphenyl)-s-triazine aswell as the instant compounds also exhibit stability against thedeleterious effects of UV light and thermal exposure.

EXAMPLE 99

The hindered amine test stabilizers are incorporated into atwo-component polyester urethane coating based on a commerciallyavailable polyester polyol (DESMOPHEN® 670-80) and commerciallyavailable isocyanurate (DESMODUR® N-3390) at a level of 2% by weightbased on total resin solids. The coating system is catalyzed with 0.015%dibutyl tin dilaurate based on total resin solids.

Each coating formulation is applied by drawdown onto transparent glassslides approximately 4″×6″ to a film thickness of about 2 mils (0.002″)in triplicate.

These triplicate glass plates are processed as seen below:

Plate 1—bake for 30 minutes at 180° F. (82° C.); age at roomtemperature; and observe daily.

Plate 2—allow to air dry (ambient cure); age at room temperature; andobserve daily.

Plate 3—allow to air dry for one day; age in a 120° F. (49° C.) oven;observe daily and continue aging at 120° F. (49° C.).

Starting at time zero, all plates are evaluated for visual appearance,noting the development of any cloudiness within the coating and anyexudate on the surface of the coating. The results of four days ofobservation are noted below.

Sample* 0 Day 1 Day 2 Day 3 Day 4 18 months Plate 1 A cl cl cl cl clclear B sl h haze haze haze haze haze C cl cl cl cl cl clear Plate 2 Acl cl cl cl cl clear B sl h haze haze haze haze haze C cl cl cl cl clclear Plate 3 A cl cl cl cl cl clear B sl h haze haze haze haze haze Ccl cl cl cl cl clear *A is unstabilized. B contains 2% by weight ofbis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate (TINUVIN ®123). C contains 2% by weight ofbis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]sebacate, compound of Example 2.

These data show that the instant compound having a hydroxy moietypresent on the group attached to the 1-position of the hindered amineprovides excellent solubility and compatibility for the polyesterurethane coating that cannot be achieved with the closest prior artcompound where said hydroxy moiety is absent.

Experience teaches that, if the instant compounds are soluble andcompatible in this particular clearcoat, they will certainly becompatible and soluble in other resin systems.

EXAMPLE 100

Approximately 50 mL of the same stabilized formulated two-componentclear coatings described in Example 99 are allowed to gel in a sealed 4ounce jar. The solidified coatings are visually observed for clarityafter solidification. The development of opacity or cloudiness isindicative of an incompatibility between the hindered amine stabilizerand the formulated coating.

Solidified coating in jar Sample* 0 Day 1 Day 2 18 months A clear clearclear clear B clear cloudy cloudy cloudy C clear clear clear clear *A isunstabilized. B contains 2% by weight ofbis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate (TINUVIN ®123). C contains 2% by weight ofbis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]sebacate, compound of Example 2.

These data show that the instant compound having a hydroxy moietypresent on the group attached to the 1-position of the hindered amineprovides excellent solubility and compatibility for the polyesterurethane coating that cannot be achieved with the closest prior artcompound where said hydroxy moiety is absent.

EXAMPLE 1011-(2-Hydroxy-2-methylpropoxy)4-[9-(methoxycarbonyl)nonanoyloxy]-2,2,6,6-tetramethylpiperidine

The title compound is prepared by the reaction of the compound preparedin Example 16A with one equivalent or more of dimethyl sebacate and acatalytic amount of lithium amide in xylene.

EXAMPLE 1021-(2-Hydroxy-2-methylpropoxy)4-[5-(methoxycarbonyl)pentanoyloxy]-2,2,6,6-tetramethylpiperidine

The title compound is made by the procedure of Example 101 wheredimethyl sebacate is replaced by an equivalent amount of dimethyladipate.

EXAMPLE 1031-(2-Hydroxy-2-methylpropoxy)-4-[3-(methoxycarbonyl)propionyloxy]-2,2,6,6-tetramethylpiperidine

The title compound is made by the procedure of Example 101 wheredimethyl sebacate is replaced by an equivalent amount of dimethylsuccinate.

EXAMPLE 1041-(2-Hydroxy-2-methylpropoxy)4-[4-(methoxycarbonyl)butyryloxy]-2,2,6,6-tetramethylpiperidine

The title compound is made the procedure of Example 101 where dimethylsebacate is replaced by an equivalent amount of dimethyl glutarate.

EXAMPLE 105 Condensation Product of4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidinewith Hexamethylene Diisocyanate, and Terminated with Methoxy

The title compound is prepared from the reaction of approximatelyequimolar amounts of the compound prepared in Example 16A withhexamethylene diisocyanate followed by reaction with excess methanol.

EXAMPLE 106 Condensation Product of4-Hydroxy-1-(2-hydroxyethoxy)-2,2,6,6-tetramethylpiperidine withHexamethylene Diisocyanate, and Terminated with Methoxy

The title compound is prepared from the reaction of approximatelyequimolar amounts of the compound prepared in Example 70 withhexamethylene diisocyanate, followed by reaction with excess methanol.

EXAMPLE 107 Condensation Product of4-Hydroxy-1-(2-hydroxy-1-phenethoxy)-2,2,6,6-tetramethylpiperidine withHexamethylene Diisocyanate, and Terminated with Methoxy

The title compound is prepared from the reaction of approximatelyequimolar amounts of the compound prepared in Example 74 withhexamethylene diisocyanate, followed by reaction with excess methanol.

EXAMPLE 108 Stabilization of a Two-Component Acrylic Urethane Clearcoat

The hindered amine test stabilizers are incorporated into atwo-component acrylic urethane coating as described om Example 99. Thesystem is catalyzed with 0.02% by weight of dibutyltin dilaurate basedon the total resin solids. The stabilizers are added at the appropriatelevel to the acrylic polyol portion of the two-component coating whichis then combined with the isocyanate component immediately prior toapplication.

Steel panels 3″×4″ primed with an electrocoat primer are then coatedwith a light blue metallic basecoat, then with the stabilized clearcoat.The basecoat is spray applied to a thickness of 1.0 mil (25 microns) dryfilm thickness and the stabilized clearcoat is then applied to athickness of 2.0 mils (50 microns) dry film thickness. The coating isair-dried and aged for two weeks. The panels are then exposed in aXenon-Arc Weather-Ometer under the following conditions:

Cam 180 cycle: 40 minutes light only; 20 minutes light and front spray;60 minutes light only; 60 minutes dark and rear spray condensate.

Lamp filters are: quartz inner/borosilicate S outer.

Irradiance: 0.45 watts per square meter.

20° Gloss is measured before exposure and at 500 hour intervals duringexposure. Higher gloss retention is desirable.

Percent Retention of 20° Gloss Sample* 4500 hours 8500 hours 12000 hoursA 17 — — B 60 22 — C 47 17 — D 34 22 — E 41 23 — F 75 45 28 G 77 45 27*A is unstabilized. B contains 1% by weight ofbis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate (TINUVIN ®123). C contains 0.9% by weight ofbis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]sebacate, compound of Example 2. D contains 1.04% by weight of2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-N-butylamino]-6-(2-hydroxyethylamino)-s-triazine.E contains 1.01% by weight of the compound of Example 12. F contains 2%by weight of bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate(TINUVIN ® 123). G contains 1.8% by weight ofbis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]sebacate, compound of Example 2.

These data show that the instant hydroxy substituted compounds givecomparable 20° Gloss Retention values to NOR compounds at equivalentmolar concentrations.

EXAMPLE 109 Stabilization of a Two-Component Acrylic Urethane Clearcoat

A clearcoat as prepared in Example 108 is applied by spin-coating to 1″silicon disks to a dry film thickness of approximately 25 microns. Theinitial optical film thickness of each disk is measured using a Zeissinterferometer. The disks are then exposed in a Xenon-Arc Weather-Ometerunder the following conditions:

Cam 180 cycle: 40 minutes light only; 20 minutes light and front spray;60 minutes light only; 60 minutes dark and rear spray condensate.

Lamp filters are: quartz inner/quartz outer.

Irradiance: 0.55 watts per square meter.

Optical film thickness is remeasured every 250 hours and film loss isdetermined for each formulation. The film loss caused by weatheringafter 3972 and 5561 hours is tabulated in the table below. A lower valuefor film loss is desirable.

Film Loss (in microns) Sample* 3972 hours 5561 hours A 23.3 completeerosion B 6.9 16.3 C 6.7 17.8 D 6.3 14.3 E 5.9 12.4 F 6.5 16.1 G 6.616.7 *A is unstabilized. B contains 1% by weight ofbis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate (TINUVIN ®123). C contains 0.9% by weight ofbis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]sebacate, compound of Example 2. D contains 1.04% by weight of2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-N-butylamino]-6-(2-hydroxyethylamino)-s-triazine.E contains 1.01% by weight of the compound of Example 12. F contains0.78% by weight of 1-octyloxy-2,2,6,6-tetramethyl-4-hydroxypiperidine. Gcontains 0.56% by weight of1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-4-hydroxypiperidine,compound of Example 16A.

These data show that the instant hydroxy substituted compounds givecomparable resistance to erosion as the closest NOR compounds atequivalent molar concentrations.

EXAMPLE 110 Coatings over Plastic Substrates

A major application for non-basic hindered amines is in the protectionof automotive topcoats applied over plastic substrates. However, manylow molecular weight, non-reactable light stabilizers migrate into theplastic substrate during drying and cure. As a consequence, asignificant portion of the light stabilizer may be lost from the topcoatinto the substrate and hence be ineffective in protecting said topcoat.

The extent of migration of hindered amine stabilizers during applicationand cure of the coating is determined by comparing the concentration ofhindered amine in the cured clearcoat applied over a plastic substrateversus the same clearcoat applied over a non-permeable substrate such asglass or steel.

Hindered amine stabilizers under test are incorporated into a flexiblethermoset acrylic/melamine clear coating appropriate for use onautomotive plastic substrates. The hindered amine is incorporated at alevel of 1.5% by weight based on total resins solids.

Each coating formulation is applied by an automatic spray apparatus ontoautomotive grade RIM (Reacting Injection Molded) substrate and TPO(thermoplastic polyolefin). Both substrates are in form of 4″×12″plaques. Each coating is applied to achieve a dry film thickness ofapproximately 2.0 mils (50 microns). The coatings are cured by baking at250° F. (121° C.) for 20 minutes.

Triplicate samples of each cured coating formulation are removed fromeach substrate and cryoground to a fine powder. A known amount of eachsample is extracted in refluxing toluene overnight. The hindered aminepresent is analyzed quantitatively by dilution to a known volume andanalyzed by HPLC or SFC chromatography. Calibration curves for each teststabilizer compound are developed. The hindered amine content of eachextracted coating is determined by this method.

When the instant hindered amine compounds substituted on the N-atom withan —O—E—OH moiety are compared to the corresponding —NOR compoundslacking such a hydroxyl moiety, a higher percent recovery of the instanthindered amine compound from the clearcoat over a plastic substrate isfound indicating that much less of the instant hindered amine stabilizermigrates into the plastic substrate allowing for better stabilization ofthe clear topcoat over such plastic substrates.

EXAMPLE 111 Stabilization of Waterborne Wood Varnish

Waterborne coating comprise a significant and increasing proportion ofthe coating in use for a wide variety of applications includingautomotive basecoats, industrial coatings and trade sale coatings. Thesecoatings may be pigmented or transparent. The trends are also towardshigher solids formulation which in general depend on light stabilizersto maintain properties on exterior exposure, and towards lower levels ofcosolvents. This requires higher solubility of stabilizers in suchcosolvents (primarily water) or actual solubility in water.

The test stabilizers are incorporated into a waterborne dispersion bypredissolution in a cosolvent blend. The waterborne dispersion is acommercially available acrylic/urethane hydrid resin. The cosolventblend is a 1:1 mixture of TEXANOL® (2,2,4-trimethyl-1,3pentanediol,Texaco) and ARCOSOLVE® TPM (tripropylene glycol methyl ether,AtlanticRichfield).

0.45 gram of the test stabilizer is predissolved in 10 g of thecosolvent blend which is then incorporated into the followingcomposition:

ppw FLEXTHANE ® 630 (Air Products) 100.0 Foamaster VF 0.1 Water 10.0TEXANOL/ARCOSOLVE/hindered amine 10.5 UV absorber (TINUVIN ® 1130, Ciba)1.2 BYK 346 0.5 MICHEMLUBE ® 162 2.0

Each coating is brush applied onto 6″×6″ sections of cedar and pineboards. The weight of the coating applied is regulated by weighing thecoating and brush before and after application and ensuring that thesame weight of coating is applied to each section.

The coated board sections are allowed to dry at ambient temperature fortwo weeks, then evaluated for visual appearance, gloss and Hunter L*, a*and b* color. The sections are exposed on racks at a 45° angle in SouthFlorida for six months before being returned and evaluated for visualappearance, gloss, color change and any other signs of degradation ordelamination.

The instant hindered amine compounds substituted on the N-atom with an—O—E—OH moiety provide better stabilization efficacy to the sections inrespect to visual appearance, gloss retention, resistance to colorchange and to delamination than do the corresponding—NOR compoundslacking such a hydroxyl moiety.

EXAMPLE 112 Stabilization of Pigmented Automotive OEM Basecoat

A basecoat pigmented with a mixture of Pigment Red 177 and mica isstabilized with 1% by weight of a hindered amine stabilizer based on thetotal basecoat solids (pigment plus resin). The basecoat is sprayapplied at a dry film thickness of 1 mil (25 microns) to primed 4″×12″steel panels, then topcoated with a high solids commercially availableautomotive clearcoat. The coated panels are cured in an over at 250° F.(121° C.) for 30 minutes. The panels are then exposed in a Xenon-ArcWeather-Ometer under the following conditions:

Cam 180 cycle: 40 minutes light only; 20 minutes light and front spray;60 minutes light only; 60 minutes dark and rear spray condensate.

Lamp filters are: quartz inner/borosilicate S outer.

Irradiance: 0.55 watts per square meter.

20° Gloss, Distinctness of Image, Hunter Color Space Values (L*, a*, b*and ΔE) are measured before exposure and after 3000 hours of exposure.

The instant hindered amine compounds substituted on the N-atom with an—O—E—OH moiety provide better stabilization efficacy to the panels inrespect to distinctness of image, gloss retention and resistance tocolor change than do the corresponding —NOR compounds lacking such ahydroxyl moiety.

EXAMPLE 113 ABS Molding Applications

Thermoplastic materials composed of mixtures of copolymers derived fromthe copolymerization of styrene monomer with acrylonitrile and thecopolymerization of stryrene monomer with butadiene, generally referredto as ABS, are dry blended with the instant compounds and meltcompounded into pellets. Typical formulations contain the instantcompounds at levels from 0.05% to 2.0%, a metal stearate such as calciumstearate at 0.05% to 0.5%, pigments from 0% to 5%, UV absorbers atlevels of 0.05% to 2.0%, phosphites at 0.0%-0.1%, phenolic antioxidantsat 0.0%-1.25%, N,N-dialkylhydroxylamine at 0.0%-0.1%, and optionallyother hindered amine stabilizers at levels of 0.0% to 2.0%.

The pelletized fully formulated resin is then processed into a usefularticle such as extrusion into sheet, film, profile and pipe; moldedinto bottles; injection molded into a molded article; thermoformed intomolded articles; or rotational molded into hollow articles.

The materials containing the instant compounds exhibit stability againstdeleterious effects of UV light and thermal exposure.

EXAMPLE 114

pK_(a) Values

In order to determine the pK_(a) values of water insoluble materials,organic references with known pK_(a) values in water are titratednon-aqueously. A plot of the half neutralization potential (HNP) versusthe known aqueous pK_(a) value of the reference material is establed.The HNP of the test material is determined and extrapolated to find thecorresponding pK_(a) value of the test material. Such organic referencematerials include 2,2,6,6-tetramethylpiperidine;4-hydroxy-2,2,6,6-tetramethylpiperidine;1-hydroxyethyl-4-hydroxy-2,2,6,6-tetramethylpiperidine; triacetoneamineand N-methylaniline.

The reference materials, which are structurally at least peripherallyrelated to the instant test materials and are soluble in both water and1:1 acetonitrile:chloroform, are used to make a calibration plot in thenon-aqueous titration (1:1 acetonitrile:chloroform solvent and 0.1Nperchloric acid/dioxane titrant) system. Approximately 0.5milliequivalents of test material is weighed into a titration beaker.Thirty mL of acetonitrile is added to dissolve the sample. Prior totitration, 30 mL of chloroform is added. Titration is carried out andthe HNP is determined. The electrolyte for the reference electrode is2-(aminomethylpyridine. The electrode is allowed to stand in the solventsystem for two hours after filling with the electrolyte to achieveequilibration. All samples are run in duplicate. The pK_(a) values areseen in the table below.

Sample* HPN (mv) Calculated pK_(a) I 523 3.9 II 436 4.9 III 513 3.8 IV —4.6 V — 3.8 VI — 4.8 *I is the compound of Example 73. II is1-cyclohexyloxy-4-ocatadecanoyloxy-2,2,6,6-tetramethylpiperidine. III isthe compound of Example 2. IV isbis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate. V is thecompound of Example 50. VI is the reaction product of2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6-chloro-s-triazinewith N,N′-bis(3-aminopropyl)ethylenediamine.

As can be seen from each of the above pairs of related compounds wherethe individual compounds differ from the other only by whether the1-position of the piperidine ring is substituted by an —O—R group or byan —O—E—OH, the instant —O—E—OH compounds consisting have asignificantly lower pK_(a) value meaning that said instant compounds aredistinguished by consistently lower basicity than the prior art N—ORcompounds.

Inspection of the results given in Example 77 shows that this lowerbasicity and lower pK_(a) values can be translated into superiorperformance for the instant compounds compared to the closely relatedprior art N—OR compounds in preventing paint loss on paintablethermoplastic polyolefins (TPO).

EXAMPLE 115 Flame Retardancy

Fiber grade polypropylene, is dry blended with the test additives andthen melt compounded at 234° C. (450° F.) into pellets. All formulationsadditionally contain melt processing stabilizer system. The pelletizedfully formulated resin is then spun at 246° C. (475° F.) into fiberusing a Hills laboratory model fiber extruder. The spun tow of 41filaments is stretch at a ratio of 1:3.2 to give a final denier of615/41.

The fibers are then knitted into socks and on a Lawson-Hemphill AnalysisKnitter. Ten replicates of each sample are tested under NFPA701-1996Vertical bum procedure. The time in seconds for the knitted sock toextinguish after the insult flame is removed is reported as “AfterFlame”. Efficacy as a flame retardant is demonstrated when low AfterFlame times are observed relative to a blank sample containing no flameretardant. The burning time of the drips from the material and theweight loss are also recorded. The data demonstrates that the instantNOR HALS are effective as flame retardants.

Additive After flame (s) Drip Burn (s) Weight loss (%) BLANK, no FR32 >50 63 Compound of 0.5 12.5 36 Example 73, 1.0%

EXAMPLE 116 Flame Retardancy of Polypropylene Thick Sections

Molding grade polypropylene is dry blended with test additives and thenmelt compounded into pellets. In addition to the instant compound,halogenated flame retardants are included in the formulation. Typicalformulations contain the instant compound and a flame retardants suchas: tris(3-bromo-2,2 bis (bromomethyl)propyl) phosphate (FMC PB370);bis(2,3-dibromopropyl ether) of bisphenol A (PE68);decabromodiphenyloxide (DBDPO); ethylene bis-tetrabromophthalimide(SATEX BT-93); ethylene bis-dibromonorbomanedicarboximide (SATEXBN-451). Other formulations may contain Sb₂O₃ in addition to thebrominated flame retardants. Other formulations may contain phosphorousbased flame retardants such as ethylene diamine diphosphate (EDAP). Thepelletized fully formulated resin is then compression molded into testspecimens using a Wabash Compression Molder.

Test plaques are tested under UL-94 Vertical bum conditions. A minimumof three replicates are tested. The average time in seconds for the testsample to extinguish after a first and second insult flame is removed isreported. Efficacy as a flame retardant is demonstrated when low Flametimes are observed. The instant compounds enhance the flame retardancyof a halogenated or phosphate flame retardant tested alone.

EXAMPLE 117 Flame Retardancy in TPO Thick Sections

Molded test specimens were prepared by injection molding thermoplasticolefin (TPO) pellets containing the instant compounds. The TPOformulations may also contain pigments, a phenolic antioxidant,phosphite or hydroxylamine, a metal stearate, ultraviolet lightabsorbers (UVA) or a hindered amine stabilizers (HALS) or a mixture ofUV absorbers and hindered amine stabilizers.

In addition to the instant compound, halogenated flame retardants areincluded in the formulation. Typical formulations contain the instantcompound and a flame retardants such as: tris(3-bromo-2,2 bis(bromomethyl)propyl) phosphate (FMC PB370); bis(2,3-dibromopropyl ether)of bisphenol A (PE68); decabromodiphenyloxide (DBDPO); ethylenebis-tetrabromophthalimide (SATEX BT-93); ethylenebis-dibromonorbomanedi-carboximide (SATEX BN451). Other formulations maycontain Sb₂O₃ in addition to the brominated flame retardants. Otherformulations may contain phosphorous based flame retardants such asethylene diamine diphosphate (EDAP).

Test plaques are tested under UL-94 Vertical bum conditions. A minimumof three replicates are tested. The average time in seconds for the testsample to extinguish after a first and second insult flame is removed isreported. The instant compounds enhance the flame retardancy of ahalogenated or phosphate flame retardant tested alone.

EXAMPLE 118 Light Stability in Flame Retardant ABS Molding Applications

Molding grade ABS is dry blended with test additives and then meltcompounded into pellets. In addition to the instant compounds, selectedflame retardants are also included. The flame retardants aretris(3-bromo-2,2-bis(bromomethyl)propyl] phosphate, decabromodiphenyloxide, ethylene bis(tetrabromophthalimide) and ethylenebis(dibromonorbomanedicarboximide). The pelletized fully formulatedresin is then injection molded into test specimens using a BOY 50Mlaboratory model injection molder. Other formulations may containantimony trioxide (Sb₂O₃) in addition to the brominated flameretardants. Other formulation may contain phosphorus based flameretardants such as ethylenediamine diphophate (EDAP).

Test plaques are mounted in metal frame and exposed in an Atlas Ci65Xenon Arc Weather-O-meter with intermittent light/dark cycles and waterspray following the ASTM G26 test procedure. Specimens are tested atperiodic intervales for changes in tensile properties and for changes incolor. The longer it takes for the loss in properties to occur and theless the color change as measured by ΔE, the more effective is thestabilizer system.

The test samples containing the instant compounds exhibit good retentionof tensile properties and minimal color change during the acceleratedweathering.

EXAMPLE 119 Light Stability in Flame Retardant HIPS Molding Applications

Molding grade high impact polystyrene is dry blended with test additivesand then melt compounded into pellets. In addition to the instantcompounds, selected flame retardants are also included. The flameretardants are tris[3-bromo-2,2-bis(bromomethyl)propyl] phosphate,decabromodiphenyl oxide, ethylene bis(tetrabromophthalimide) andethylene bis(dibromonorbomanedicarboximide). The pelletized fullyformulated resin is then injection molded into test specimens using aBOY 50M laboratory model injection molder. Other formulations maycontain antimony trioxide (Sb₂O₃) in addition to the brominated flameretardants. Other formulation may contain phosphorus based flameretardants such as ethylenediamine diphophate (EDAP).

Test plaques are mounted in metal frame and exposed in an Atlas Ci65Xenon Arc Weather-O-meter with intermittent light/dark cycles and waterspray following the ASTM G26 test procedure. Specimens are tested atperiodic intervales for changes in tensile properties and for changes incolor. The longer it takes for the loss in properties to occur and theless the color change as measured by ΔE, the more effective is thestabilizer system.

The test samples containing the instant compounds exhibit good retentionof tensile properties and minimal color change during the acceleratedweathering.

EXAMPLE 120 Stabilization of High Solids Acid-catalyzed ThermosetAcrylic Resin Enamel

A high solids (50% by weight) thermoset acrylic resin enamel, catalyzedby 0.8% by weight of dodecylbenzenesulfonic acid, based on thefilm-forming resin is stabilized by the addition of various instantcompounds. The high solids thermoset acrylic resin enamel formulation(Acryloid AT 400 from Rohm and Haas) is based on hydroxyethylmethacrylate, methyl methacrylate, styrene, butyl acrylate and butylmethacrylate and a melamine curing agent.

Pieces of steel sheeting 4″×12″ (9.16 cm×30.48 cm), coated with a primerbased on polyester/epoxy resin, are then coated with a TiO₂-pigmentedbase coat based on a binder of 70% of monomers such as hydroxyethylacrylate, styrene, acrylonitrile, butyl acrylate and acrylic acid with30% of a melamine resin and an acid catalyst and finally with a clearfinishing enamel. The base coat is sprayed onto the sheet to a thicknessof about 0.8 mil (0.0203 mm) and air dried for three minutes. The clearfinishing enamel is then sprayed onto the sheet to a thickness of about2.0 mil. After 15 minutes air-drying, the coated sheets are baked for 30minutes at 121° C.

The stabilizers under test are added to the thermoset acrylic resinfinishing enamel in a concentration of 1% by weight before the enamel iscoated onto the base coat.

The coated sheets, after storage for three weeks in an air-conditionedroom (23° C./50% relative humidity), are subjected to weathering for2000 hours according to SAE J1920 in a Xenon arc Weather-Ometer. In thisapparatus, samples are subjected to weathering in repeated cycles of 180minutes. The effectiveness of the stabilization is measured by theretention of 20° gloss after weathering.

The sheets stabilized by the instant compounds exhibit good retention of200 gloss after weathering under extreme weather conditions.

EXAMPLE 121

The samples prepared in Example 120 are also evaluated on the basis ofKnoop Hardness (ASTM D-147468) on baked and overbaked samples; on thedistinction of image (DOI); on Hunter Associates Apparatus; on 20° gloss(ASTM D-523-80); and on cracking based on visual observation.

The samples stabilized by the instant compounds exhibit a pattern ofgreater retention of 20° gloss and DOI, and a longer absence of severecracking after exposure.

EXAMPLE 122

The thermoset acrylic enamel of Example 120 is formulated to include 3%by weight of a benzotriazole UV absorber and 1.5% by weight of aninstant hindered amine test compound. The enamel is coated over a whitebase coat or over a silver metallic base coat. Baking is conducted at121° C. normal bake or at 82° C. automotive low bake repair temperature.

The coated panels are exposed in a Xenon arc exposure apparatus and 20°gloss and distinction of image (DOI) values are determined.

The samples stabilized by the instant compounds exhibit a pattern ofgreater retention of 20° gloss and DOI.

EXAMPLE 123

Two thermoset acrylic enamles are formulated to include 3% by weight ofa benzotriazole UV absorber and 1% by weight of an instant hinderedamine test stabilizer.

The thermoset acrylic enamels are based on a binder of 70% of monomerssuch as hydroxyethyl acrylate, styrene, acrylonitrile, butyl acrylateand acrylic acid with 30% of a melamine resin and an acid catalyst suchas p-toluenesulfonic acid, dinonylnaphthalene-disulfonic acid,dodecylbenzenesulfonic acid or phenyl acid phosphate.

Pieces of steel sheeting 4″×12″ (9.16 cm×30.48 cm), coated with a primerbased on polyester/epoxy resin, are then coated with a base coat andfinally with a clear finishing enamel. The base coat is sprayed onto thesheet to a thickness of about 0.8 mil (0.0203 mm) and air dried forthree minutes. The clear finishing enamel is then sprayed onto the sheetto a thickness of about 2.0 mil. After 15 minutes air-drying, the coatedsheets are baked for 30 minutes at 121° C.

The coated panels are exposed in a Xenon arc exposure apparatus and 20°gloss and distinction of image (DOI) values are determined.

The samples stabilized by the instant compounds exhibit a pattern ofgreater retention of 20° gloss and DOI.

EXAMPLE 124

A white polyester/melamine based oil-free alkyl coil coating is utilizedin this example. The fully formulated paint is applied over a primedsteel sheet using a wire wound rod to give 0.6-0.8 mil dry film. Thepanels are baked for about 90 seconds at 220° C., removed from the ovenand immediately quenched in water. The coated panels are exposed in aXenon Arc Weather-Ometer, and in South Florida at an angle of 45° S tothe sun. 20° gloss values are determined.

The samples stabilized by the instant compounds exhibit a pattern ofgreater retention of 20° gloss.

EXAMPLE 125

The thermoset acrylic enamel of Example 124 including 0.8%dodecylbenzenesulfonic acid is formulated to include varyingconcentrations of benzotriazole or s-triazine UV absorbers and theinstant hindered amine test compounds. The enamel is coated over asilver metallic base coat pursuant to the procedure of Example 124 andbaking is conducted for 30 minutes at 121° C. the normal backetemperature.

The coated panels are exposed in a Xenon arc Weather-Ometer and the timeto the 50% loss of 20° gloss is determined.

The samples stabilized by the instant compounds and a UV absorberexhibit an excellent retention of 20° gloss and a much longer time till50% loss in 20° gloss is observed.

EXAMPLE 126

A thermoset acrylic enamel based on a binder of 70% of monomers such ashydroxyethyl acrylate, styrene, acrylonitrile, butyl acrylate andacrylic acid with 30% of a melamine resin and an acid catalyst such asp-toluenesulfonic acid, dinonylnaphthalenedisulfonic acid ordodecylbenzenesulfonic acid is formulated. Commercially available 9.16cm×30.48 cm Uniprime panels are used as the substrate. The panels arecoated with a silver metallic base coat and then with a clear finishingenamel. The base coat is stabilized with 1% of a benzotriazole UVabsorber and 1% of an instant hindered amine test compound (based onsolid resin) and is sprayed onto the panel to a thickness of about0.6-0.8 mil and air dried for three minutes. The clear coat includingthe above-noted stabilizers is then sprayed to a thickness of 1.7-2.0mils and after 10 minutes of air drying, the coated panels are baked for30 minutes at 121° C. The coated panels are then exposed in a Xenon arcapparatus and the 20° gloss values are determined.

The samples stabilized by the instant compounds and a UV absorberexhibit excellent retention of 20° gloss.

EXAMPLE 127

A water-borne acrylic melamine enamel is formulated as seen below:

Parts Resin Solids Synthacryl VSW 6483 30 (acrylic dispersion fromHoechst) Synthacryl VSW 6484 42 (50% acrylic resin in butyl diglycol,Hoechst) Maprenal MF 915 25 (70% melamine resin in isobutanol) MaprenalMF 927 3 (melamine resin) 100

A water-based base coat/clear coat enamel is prepared by spray applyinga 0.6-0.8 mil thick film of commercial silver metallic waterborne basecoat (from BASF) over an epoxy primed coil coated aluminum panel. Thismaterial is baked at 80° C. for five minutes and then clear coated with1.6-1.8 mil of the waterborne enamel. The system is baked at 80° C. forten minutes and then at 140° C. for a further 30 minutes. Prior toapplication of the clear coating, instant test and light stabilizersdissolved in a minimum amount of butyl glycol acetate are added to thepaint. The coated panels are exposed in a Xenon arc apparatus for 975hours. The distinction of image (DOI) retention of the panels ismeasured.

The samples stabilized by the instant compounds exhibit greaterretention of DOI values.

EXAMPLE 128 Stabilization of Tung Oil Phenolic Varnish

Pieces of 1.27 cm×20.32 cm×30.48 cm western red cedar panels having afine radial cut are used to test a commercially available tung oilphenolic varish (supplied by McCloskey). One half of each panel iscoated with two coats of unstabilized varnish. An equal amount ofvarnish containing 5% by weight (based on resin solids) of teststabilizers is applied to the other half of the panel in two coats.After storage for two weeks at ambient temperature, the wood panels areexposed outdoors at an angle of 45° S for a period of eight months. The60° gloss of each half of the panel is measured at the top, middle andbottom portion of the panel and averaged according to ASTM D 523. Due tothe lack of homogeneity of wood substrates, the gloss retention of thesame varnish tends to differ slightly from panel to panel. Thus, theapplication of an unstabilized control varnish to every panel allows fora more meaningful measurement of the improvement in gloss due to thepresence of the instant test compound.

The panels stabilized by the instant compounds show excellent glossretention after long exposure.

EXAMPLE 129 Stabilization of an Aromatic Urethane Varnish

A sample of commercial aromatic urethane varnish (Flecto-Varathane #90)is tested by the same method described in Example 128. After outdoorexposure at an angle of 45° S for a period of five months, the 60° glossretention values of unstabilized and stabilized portions of the panelsare determined.

The panels stabilized by the instant compounds show excellent glossretention.

EXAMPLE 130 Stabilization of a White Two-Component Polyester UrethaneGloss Enamel

A white polyester is formulated as shown below:

Parts Component I Desmophen 670-90 (polyester glycol, Mobay) 132.4Titanium Dioxide 198.6 Cellosolve Acetate 98.9 Sand Mill Desmophen670-90 94.98 Flow Aid 0.28 Tertiary Amine 0.015 Cellosolve Acetate 332.6Component II Desmodur N-100 (polyisocyanate, Mobay) 93.9 CellosolveAcetate 58.7

This material is spray applied at a dry film thickness of 1.5-2.0 milonto Bonderite 40 cold rolled steel panels that have been previouslyprimed with a commerical epoxy polyamide maintenance primer(Sherwin-Williams Tile Clad II). Prior to application, the instant testcompounds are added to the paint. After ambient storage for two weeks,three panels of each formulation are exposed outdoors at an angle of 45°S for a period of nine months. Thereafter, 20° gloss retention isdetermined by ASTM D 523-80 at the top, middle and bottom portions ofeach panel. Thus, the average values for nine gloss retentionmeasurements for each triplicate set of panels are obtained.

The panels stabilized by the instant compounds show excellent glossretention.

EXAMPLE 131 Stabilization of Acrylic Alkyd Refinish Enamel

A commercially available acrylic alkyd enamel pigments with non-leafingaluminum pigment and tinted a light blue is stabilized with abenzotriazole UV absorber and an instant hindered amine test compoundand is then spray applied onto Bonderite 40 panels primed with an alkydprimer. After the coating is allowed to cure at room temperature for 14days, the panels are exposed outdoors at an angle of 45° S for a periodof eight months. The 20° gloss of the exposed panels is measured.

The panels stabilized by the instant compounds show excellent glossretention.

EXAMPLE 132 Stabilization of a Medium Oil Alkyd Enamel

A medium oil alkyd enamel pigmented with a non-leafing aluminum pigmentand tinted light blue is stabilized with a benzotriazole UV absorber andan instant hindered amine test compound and is then sprayed applied ontocold rolled steel panels primed with an epoxy primer. After the coatingis allowed to cure at room temperature for two weeks, the panels areexposed for accelerated weathering in a Xenon Arc Weather-Ometer for 840hours. The 20° gloss values of the panels are determined before andafter exposure.

The panels stabilized by the instant compounds show excellent glossretention.

EXAMPLE 133 Electrocoat Composition

A typical E-coat composition is prepared by adding the diglyicidyl etherof bisphenol A, polyethylene oxide diol, bisphenol A and xylene to aflask and heating to 135° C. The catalyst dimethylbenzylamine in xyleneis added and the temperature maintained at 143° C. for two hours. Theweight per epoxy (WPE) is measured and a previously prepared crosslinkercomposed of 2,4-toluenediisocyanate, trimethylolpropane blocked with analcohol is then added and temperature reduced to 100° C. The remainingepoxy groups are then capped with two different secondary amines, namelydiketimine of diethylenetriamine and methylethanolamine, in phenylcellosolve. The temperature is maintained for one hour at 110° C. andthe crosslinker hexamethylenediisocyanate blocked with an alcohol isadded. The temperature is maintained near 100° C. for 30 minutes and theresin mixture is added to deionized water, surfactant and lactic acid togive a resin emulsion.

To this resin emulsion is added the instant hindered amine compound,additional epoxy resin, carbon black, dibutyltin oxide catalyst,titanium dioxide, lead silicate, water and UV absorber. After dispersionusing a sand mill to achieve proper fineness, the mixture isincorporated into an electrocoat bath with water for electrocoating ontoa metal substrate.

The steel coating electrocoated with the above E-coat resin compositionto a thickness of 23-30 μm and cured for 20 minutes at a temperature of176-201° C. A pigmented resin layer is coated thereover at a thicknessof 20-51 μm using an acrylic coating composition in an organic solver,pigments and a UV absorber. The coated panels are then baked at 121-129°C. to cure the pigmented layer.

The panels are then exposed outdoors for four months. The panelscontaining the instant hindered amine compound, particularly when usedwith a UV absorber, provided excellent resistance to delamination of theE-coat layer from the metal substrate.

EXAMPLE 134 Abrasion-Resistant Coating Compositions

A solution in isopropanol of 50% (by weight) of 1,6-hexanediol, 10%3-methacryloyloxy-propyltrimethoxysilane and 40% colodial silica (inform of a 34% aqueous dispersion) is vacuum stripped to remove volatilesand combined with an instant hindered amine compound, a benzotriazole UVabsorber and 2,4,6-trimethylbenzoyldiphenylphosphine photoinitiator.These compositions show no gelation on storage.

The compositions above are applied by roller coating to a 15 mil film ofbisphenol A polycarbonate and the coated films are passed under amercury lamp at 43° C. at a line speed of 610 cm/min. The compositionsare cured to a colorless and optically clear coatings over thepolycarbonate substrate.

The coatings as measured by the Taber Abrasion Test (ASTM D1044) areabrasion resistant.

The test specimens are also subjected to accelerated aging tests usingan Atlas Ci35A Xenon Arc Weather-Ometer. The results show that thecoatings containing the instant hindered amine compound exhibitexcellent resistance to yellowness and haze formation.

EXAMPLE 135 Coating over Polycarbonate

A two-component polyester urethane coating is stabilized by the additionof an instant hindered amine compound. The high-solids polyester polyol(Desmophen 670-80, Bayer) is crosslinked with an isocyanate based resin(Desmodue N-3390, Bayer). The coating is catalyzed with 0.015% by weightof dibutyltin dilaurate catalyst.

Plaques of polycarbonate-based plastic substrate (Xenoy) 4″×6″ arecoated with the formulated clear coat at a thickness of approximately1.5 mils. The coating is spray applied to the substrate and then bakedat 82° C. for 20 minutes.

After storage for one week at room temperature, each plaque is cut into2″×3″ strips with five replicates being made for each formulation. Eachstrip is placed into a 8-oz jar along with 2 mL of distilled water andsealed. All samples are placed in an over at 54° C. A crosshatchadhesion test is performed once a week on at least two of the replicatesamples until the sample failed (5% adhesion loss) or until 40 dayselapses.

The samples containing the instant hindered amine compounds exhibitexcellent resistance to delamination.

What is claimed is:
 1. A compound of formula (29), which compound is thecondensation product of a dialkyl ester or diisocyanate with a hydroxysubstituted N-alkoxy derivative of 4-hydroxy-2,2,6,6-tetramethylpiperidine

wherein G₁ to G₂ are independently alkyl of 1 to 4 carbon atoms, or G₁to G₂ together are pentamethylene; z is an integer such that thecompound has a molecular weight of 1000 to 4000 amu; G is straight orbranched chain alkylene of 1 to 18 carbon atoms, cycloalkylene of 5 to 8carbon atoms, cycloalkenylene of 5 to 8 carbon atoms, alkenylene of 3 to18 carbon atoms, a straight or branched chain alkylene of 1 to 4 carbonatoms substituted by phenyl or by phenyl substituted by one or two alkylof 1 to 4 carbon atoms, with the proviso that in formula (29) successivehindered amine moieties can be oriented in either a head to head or headto tail fashion;

R₂₇ is a straight or branched chain alkylene of 1 to 18 carbon atoms,cycloalkylene or cycloalkenylene of 5 to 8 carbon atoms, phenylene,—NH-alkylene-NH— of 2 to 18 carbon atoms, 5-imino-1-iminomethyl-1,3,3-trimethylcyclohexane or —NH-xylylene-NH—; andR₂₈ is alkyl of 1 to 4 carbon atoms,


2. A compound according to claim 1 wherein G₁ and G₂ are each methyl. 3.A compound according to claim 1 where in formula (29), R₂₇ is ethylene,trimethylene, tetramethylene, octamethylene, 1,6-diaminohexane or5-amino-1-aminomethyl-1,3,3-trimethylcyclohexane; z is an integer suchthat the molecular weight of the compound is 1500-3000 amu; R₂₈ ismethyl or ethyl; and G is ethylene, 1,2-cyclohexanediyl,1,3-cyclohexanediyl, 1,4-cyclohexanediyl, —CH(C₆H₅)CH₂— or —CH₂C(CH₃)₂—.4. A compound according to claim 1 where in formula (29), R₂₇ isethylene, trimethylene, tetramethylene or octamethylene; z is an integersuch that the molecular weight of the compound is 1500 to 2000 amu; andR₂₈ is methyl.
 5. A compound according to claim 1 where in the compoundof formula (29), —G—O— is —CH₂C(CH₃)₂—O—.
 6. A compound according toclaim 1 which is (m) condension product of4-hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidinewith hexamethylene diisocyanate and terminated with methoxy; (n)condension product of4-hydroxy-1-(2-hydroxyethoxy)-2,2,6,6-tetramethylpiperidine withhexamethylene diisocyanate and terminated with methoxy; or (o)condension product of4-hydroxy-1-(2-hydroxy-2-phenethoxy)-2,2,6,6-tetramethylpiperidine withhexamethylene diisocyanate and terminated with methoxy.